Thermoresponsive brush polymers with copolymer backbone and copolymer arms

Abstract

This specification relates to a brush copolymer composition comprising: a copolymer backbone comprising monomer repeat units of at least two different acrylate monomers and copolymer brush arms comprising monomer repeat units of at least two different acylated poly(alkylene amine)s, wherein the brush arms, the brush copolymer, or both can advantageously exhibit UCST behavior, for example, in a hydrocarbon diluent. Methods of making such copolymers using (pseudo)living reactions of RAFT and CROP are also described herein.

Description

Technical Field

[0001] This disclosure generally relates to brush copolymers having a copolymer backbone and copolymer brush arms. The copolymer brush arms and / or the brush copolymer itself may exhibit upper critical solution temperature (UCST) behavior in relatively nonpolar diluents. Such brush copolymers can be used to modify the viscosity of compositions such as lubricant compositions (e.g., for passenger car, heavy-duty diesel engines, and / or marine diesel engines) or other functional fluids (e.g., manual / automatic transmission fluids). More specifically, such brush copolymers may have a poly(meth)acrylate copolymer backbone grafted with acylated poly(alkylene amine) copolymers, such as polyoxazoline. Lubricant compositions containing such brush copolymers and methods for manufacturing such brush copolymers are also described herein. Background Technology

[0002] Since the first reports of the living cationic ring-opening polymerization (CROP) of 2-oxazolines by four independent research groups in 1966 (T. Kagiya et al., Ring-Opening Polymerization of 2-Substituted 2-Oxazolines. J. Polym. Sci. Part B Polym. Lett., 1966, 4(7), 441-445; W. Seeliger et al., Recent Syntheses and Reactions of Cyclic Imidic Esters. Angew. Chem. Int. Ed. Engl., 1966, 5(10), 875-888; DATomalia et al., Homopolymerization of 2-alkyl- and 2-aryl-2-oxazolines. J. Polym. Sci. Part A-1 Polym. Chem., 1966, 4(9), 2253-2265; and TGBassiri et al., Polymerization of Cyclic Imino Ethers.I.Oxazolines.J.Polym.Sci.Part B Polym.Lett.,1967,5(9),871-879), 2-oxazoline monomers and their corresponding poly(2-alkyl-2-oxazoline) have received increasing attention for the development of high-performance polymer materials, especially for biomedical applications.

[0003] Under appropriate conditions, CROP of 2-oxazoline can proceed in a living or quasi-living fashion according to the typical mechanism of chain growth polymerization. B. Verbraeken et al., The Chemistry of Poly(2-oxazoline)s. Eur. Polym. J., 2017, 88, 451-469. The living nature of this polymerization allows for the synthesis of not only well-defined homopolymers but also well-defined random and block copolymers, depending on the reactivity of the 2-oxazoline monomer. S. Kobayashi et al., Block Copolymers from Cyclic Imino Ethers: A New Class of Nonionic Polymer Surfactant. Macromolecules, 1986, 19(3), 535-541; T. Saegusa et al., One-Shot Block Copolymerization. Makromol. Chem. Macromol. Symp., 1990, 31(1), 1-10.

[0004] Furthermore, by changing the substituents at the 2-position of the 2-oxazoline ring, the structure and physical properties of poly(2-alkyl-2-oxazoline) can be precisely adjusted and regulated according to the desired application. Besides linear (co)polymers, different structures obtained by copolymerization with other monomers have been described in the literature (e.g., E. Rossegger et al., Design Strategies for Functionalized Poly(2-oxazoline)s and Derived Materials. Polymers, 2013, 5(3), 956-1011; H. Schlaad et al., Poly(2-Oxazoline)s as Smart Bioinspired Polymers. Macromol. Rapid Commun., 2010, 31(6), 511-525; D. Pizzi et al., Poly(2-Oxazoline) Macromonomers as Building Blocks for Functional and Biocompatible Polymer Architectures. Eur. Polym. J., 2019, 121, 109258). Among them, brush-like and grafted (co)polymers are particularly interesting because the properties of different polymer units can be combined within the same molecule, thus opening up possibilities for various potential applications. Three synthetic methods can be used to synthesize graft copolymers: (i) Grafting-through, (ii) Grafting-from, and (iii) Grafting-onto.

[0005] However, grafted structures based on poly(2-alkyl-2-oxazoline) are rare. They are mainly synthesized via a grafting-through method, in which the active oxazoline compounds are end-capped with (meth)acrylate and then (co)polymerized with other monomers.

[0006] On the one hand, the use of living polymerization offers many advantages (i.e., good control over the molecular weight, dispersity values, and macromolecular structure of the resulting polymers, well-defined end groups, and the possibility of easily synthesizing block copolymers). On the other hand, a wide variety of monomers can be (co)polymerized via conventional free radical polymerization due to easy reaction conditions and high tolerance to many functional groups. However, well-defined (co)polymers are generally not obtainable via free radical polymerization due to termination reactions (A. Rudin et al., Free-Radical Polymerization). The Elements of PolymerScience&Engineering(3rd edition; Academic Press: 2013; pp. 341-389). Therefore, the development of methods that combine the advantages of living polymerization with the versatility of free radical polymerization is considered of great interest in the field of polymer chemistry.

[0007] The three main mechanisms of controlled radical polymerization (CRP) are: (i) nitroxide-mediated polymerization (NMP), (ii) atom transfer radical polymerization (ATRP), and (iii) reversible addition-fragmentation chain-transfer (RAFT) polymerization. Among these, RAFT polymerization is considered one of the most powerful and versatile methods for providing reactive properties to radical polymerization. RAFT polymerization generally tends to have relatively easy reaction conditions and relatively high functional group tolerance, which allows for the polymerization of a wide variety of monomers (more so than NMP and ATRP) over a wide temperature range and in a large number of solvents. Therefore, the combination of CROP and RAFT polymerization techniques, as described in this paper, can provide a powerful tool for obtaining well-defined polymers based on poly(2-alkyl-2-oxazoline) and RAFT monomers with precise structures.

[0008] The ability to combine hydrophilic and hydrophobic monomers into well-defined polymers with specific macromolecular structures opens up a wide range of potential applications, especially due to their amphiphilic properties, which can lead to self-assembly into nanoscale objects in solution. Their self-assembly behavior can also be triggered by external stimuli, making them valuable and versatile candidates for a broad range of applications. Temperature-responsive polymers are of particular interest due to their potential applications in the biomedical field, as well as in water recycling strategies and architecture.

[0009] However, the temperature response behavior of linear (co)polymers and (co)polymers with more complex structures has been studied, especially in pure water or alcohol / water mixtures. In fact, only a limited number of studies have reported on polymers exhibiting thermal responsiveness in non-aqueous media.

[0010] It has been observed that linear poly(octadecyl vinyl ether) can undergo an upper critical solution temperature (UCST) phase transition of approximately 30 °C in various solvents due to the crystallization of long alkyl chains (T. Yoshida et al., Stimuli-Responsive Reversible Physical Networks. I. Synthesis and Physical Network Properties of Amphiphilic Block and Random Copolymers with Long Alkyl Chains by LivingCationic Polymerization. J. Polym. Sci. Part A Polym. Chem., 2005, 43(6), 1155-1165).

[0011] Block copolymers of polystyrene and polyisoprene can form cylindrical micelles or vesicles in heptane at room temperature, depending on the length of the isoprene blocks, and these micelles can reversibly transform into spherical or cylindrical micelles, respectively, upon heating to ~40°C. Poly(styrene-dimethylsiloxane) diblock copolymers can self-assemble into vesicles in various dialkyl phthalates at room temperature. With increasing temperature and thus decreasing solvent selectivity, a reversible morphological transition from vesicles to cylinders to spherical micelles can be observed.

[0012] Poly(lauryl methacrylate-block-styrene-block-lauryl methacrylate) gradient copolymers can form spherical colloidal micelles in commercially available aliphatic oils, which swell as the temperature increases due to the gradual solubilization of the mixing domains of the two blocks.

[0013] It has been shown that the worm phase obtained by polymerization-induced self-assembly (PISA) of a diblock copolymer of benzyl methacrylate and lauryl methacrylate can form a soft, free-standing gel in n-dodecane at ~20 °C. This gel can degellate upon heating above ~50 °C due to the worm-to-sphere transition, which appears to be irreversible in dilute solutions (~0.10% w / w), but may become reversible with increasing polymer concentration (~20% w / w).

[0014] A block copolymer of octadecyl methacrylate and 3-phenylpropyl methacrylate can form a pure worm phase in n-octane, resulting in a physical gel at room temperature. Upon heating, this gel can become a free-flowing solution, presumably due to a morphological transformation from worms to spherical nanoparticles caused by solvation changes in the 3-phenylpropyl methacrylate blocks.

[0015] All-acrylic diblock copolymer nanoparticles composed of lauryl acrylate and benzyl acrylate can also exhibit similar behavior in n-dodecane. Recently, the thermal response behavior of diblock copolymer vesicles of octadecyl methacrylate and benzyl methacrylate prepared directly from mineral oil via PISA has been investigated. Again, in this case, the diblock copolymer can undergo a vesicle-to-worm phase transition upon heating.

[0016] UCST-type behavior has been observed in homopolymers and random copolymers of alkyl methacrylate monomers with appropriate alkyl side chain lengths in polyalphaolefins (PAOs). Furthermore, a series of ABA triblock copolymers containing PAO-loving mesoblocks and temperature-responsive exoblocks have been synthesized via RAFT polymerization using bifunctional chain transfer agents. At appropriate block compositions and concentrations, these triblock copolymers appear to exhibit tunable thermally reversible sol-gel transitions.

[0017] Graft copolymers composed of polyolefin backbones grafted with butyl methacrylate and lauryl methacrylate can exhibit UCST behavior in n-dodecane: at low temperatures, clusters containing methacrylate-rich domains can be observed due to the low solubility of the side chains, while at high temperatures, deaggregation into single chains seems to be promoted due to the increased solubility of the methacrylate side chains.

[0018] Finally, the solution behavior of linear polydimethylsiloxane-poly(2-(dimethylamino)ethyl methacrylate) diblock copolymer in decamethylcyclopentasiloxane silicone oil was recently investigated: the diblock copolymer appears to undergo a worm-to-sphere transformation upon heating, induced by reversible solvent plasticization of the poly(2-(dimethylamino)ethyl methacrylate) core.

[0019] Similarly, in the case of poly(2-alkyl-2-oxazoline)-based materials, their tunable thermal response behavior has been studied only in pure water or water / alcohol mixtures. For example, the temperature response behavior of homopolymers of 2-ethyl-2-oxazoline and 2-isopropyl-2-oxazoline has been extensively reported. It has been shown that they have a lower critical solution temperature (LCST) in aqueous solution (P. Lin et al., Solubility and Miscibility of Poly(Ethyl Oxazoline). Polym. Phys., 1988, 26(3), 603-619; U. Hiroshi et al., A Novel Thermo-Sensitive Polymer. Poly(2-Iso-propyl-2-Oxazoline). Chem. Lett., 1992, 21(9), 1643-1646; C. Diab et al., Microcalorimetric Study of the Temperature-Induced Phase Separation in Aqueous Solutions of Poly(2-Isopropyl-2-Oxazolines). Macromolecules, 2004, 37(7), 2556-2562; JSPark et al., Versatile Synthesis of End-Functionalized Thermosensitive Poly(2-Isopropyl-2-Oxazolines).Macromolecules, 2004, 37(18), 6786-6792; M.Meyer et al., Unexpected Thermal Characteristics ofAqueous Solutions of Poly(2-Isopropyl-2-Oxazoline).Soft Matter, 2007, 3 (4), 430-431; S. Huber et al., Effect of End Group Polarity Upon the Lower Critical Solution Temperature of Poly(2-Isopropyl-2-Oxazoline). Colloid Polym. Sci., 2008, 286 (14-15), 1653-1661; Y. Jung et al., Linear and Cyclic Poly(2-Isopropyl-2-Oxazoline)s for Fine Control of Thermoresponsiveness. Eur. Polym. J., 2017, 88, 605-612). LCST can be modified and precisely controlled by copolymerizing 2-oxazoline monomers with different alkyl side chain lengths and therefore different hydrophilicity / hydrophobicity ratios.

[0020] To enhance the properties of the final materials and better control the temperature range of the phase transition, more complex structures have also been investigated. Among these, comb-type and graft copolymers based on poly(2-alkyl-2-oxazoline) exhibiting tunable LCST in aqueous solutions are of great interest due to the aforementioned application potential. However, despite extensive work on 2-oxazoline polymers exhibiting LCST behavior, few polyoxazolines have been reported to exhibit upper critical solution temperature (UCST) phase transitions, and those reported occur only in alcohol / water mixtures. HML Lambermont-Thijs et al., Solubility Behavior of Amphiphilic Block and Random Copolymers Based on 2-Ethyl-2-Oxazoline and 2-Nonyl-2-Oxazoline in Binary Water-Ethanol Mixtures.J.Polym.Sci.Part APolym.Chem.,2009,47(2),515-522.81,89-91; HML Lambermont-Thijs et al., Temperature Induced Solubility Transitions of Various Poly(2-Oxazoline)s inEthanol-Water Solvent Mixtures.Polymers, 2010, 2(3), 188-199; R.Hoogenboom et al., ASchizophrenic Gradient Copolymer: Switching and Reversing Poly(2-Oxazoline)Micelles Based on UCST and Subtle Solvent Changes.Soft Matter, 2009, 5 (19), 3590-3592; R. Hoogenboom et al., Tuning Solution Polymer Properties by BinaryWater-Ethanol Solvent Mixtures. Soft Matter, 2008, 4 (1), 103-107.

[0021] As further described herein, brush arm copolymers (and even some linear homopolymers) of 2-stearyl-2-oxazoline (SteOx) and 2-ethyl-2-oxazoline (EtOx), as well as other oxazoline monomers, were synthesized via active CROP to obtain well-defined polymers with different polarities and oil solubility. Additionally, a grafted brush arm copolymer (poly(xMA)) with a random copolymer backbone of methacrylate-(2-ethylhexyl) methacrylate obtained by RAFT polymerization was reacted with the brush arm copolymer side chains (polyOx) using a Grafting-onto method. The 2-oxazoline copolymer and the grafted brush arm copolymer were evaluated in commercially available oils (e.g., Yubase) using turbidity measurements and thermal analysis. TM Solubility behavior in 4). This is believed to be the first example of thermoresponsive linear copolymers and grafted brush copolymers based on 2-oxazoline and methacrylate monomers exhibiting UCST-type phase transitions in pure non-aqueous systems.

[0022] This disclosure also provides the use of the brush copolymer compositions according to this disclosure for modifying the turbidity, thermal properties and / or viscosity properties of lubricant compositions.

[0023] Detailed Explanation

[0024] This disclosure relates to brush copolymers, methods of manufacturing them, and their application / use, for example, as lubricant components and / or in lubricant compositions. The brush copolymers disclosed herein have a copolymer backbone and copolymer brush arms.

[0025] The copolymer brush arm may comprise, consist essentially of, or be composed of repeating units of at least two different acylated poly(alkyleneamine) monomers of formulas (1) and (2), respectively.

[0026]

[0027] In equations (1) and (2), each R 5 It can be independently hydrogen or linear or branched C1-C 24 Alkyl structural moiety (especially linear or branched C2-C) 18 Alkyl structure moiety), and each R 6 —Different from each R 5 Despite having similarities with each R 5 Same or greater carbon number – can be independently linear or branched C8-C 24 Alkyl structural moieties (especially linear or branched C8-C) 20Alkyl structure portion). In these formulas, the subscripts y and z can each be 1 or 2 (in particular, the subscripts y and z can both be 1). Due to the typical similarity (although not exactly the same) between the monomer repeating units of formulas (1) and (2), it is believed that the brush arm can be a random (or near-random) copolymer, but in any case not a block copolymer, and generally does not have high block copolymer characteristics.

[0028] As used herein, the term "alkyl" in relation to hydrocarbons should be understood to distinguish non-aromatic, heteroatomless hydrocarbons from aromatic hydrocarbons and heteroatom-containing hydrocarbons. Therefore, the term "alkyl" can be defined as including cycloalkyl groups, alkenyl groups having one or more carbon-carbon double bonds (including or excluding any cyclic groups; also including conjugated double bonds, provided that the conjugation does not form an aromatic conjugation), and alkynyl groups having one or more carbon-carbon triple bonds (including or excluding any carbon-carbon double bonds and / or any cyclic groups). As is known to those skilled in the art, in hydrocarbon materials, "heteroatom" represents an atom that is neither hydrogen nor carbon, which may include, but is not necessarily limited to, oxygen, nitrogen, sulfur, phosphorus, selenium, halogens, metalloids (such as boron, silicon, germanium, arsenic, antimony, tellurium, etc.), metals (such as alkali metals, alkaline earth metals, transition metals, lanthanides, actinides, aluminum, gallium, indium, lead, tin, bismuth, etc.), and noble gases. However, in some implementations, the term "alkyl" may be limited to acyclic, single-carbon-carbon bonded hydrocarbons.

[0029] In embodiments where the brush arm consists solely of monomers of formulas (1) and (2), the sum of the subscripts m and n naturally represents 100 mol% of the average degree of polymerization of the copolymer brush arm. However, in embodiments where the brush arm comprises or is substantially composed of monomers of formulas (1) and (2), the sum of m+n may be 60 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arm (e.g., 60 mol% to 99 mol%, 60 mol% to 95 mol%, 60 mol% to 90 mol%, 60 mol% to 85 mol%, 60 mol% to 80 mol%, 70 mol% to 100 mol%, 70 mol% to 99 mol%, 70 mol% to 95 mol%, 70 mol% to 90 mol%, 70 mol% to 85 mol%). 70 mol% to 80 mol%, 80 mol% to 100 mol%, 80 mol% to 99 mol%, 80 mol% to 95 mol%, 80 mol% to 90 mol%, 90 mol% to 100 mol%, 90 mol% to 99 mol%, 90 mol% to 95 mol%, 95 mol% to 100 mol%, 95 mol% to 99 mol%, or 99 mol% to 100 mol%; particularly 90 mol% to 100 mol%, 95 mol% to 100 mol%, or 99 mol% to 100 mol%.

[0030] Additionally or alternatively, the average degree of polymerization of the brush arm and / or the sum of m+n may be 100 or less (e.g., 85 or less, 75 or less, 65 or less, 60 or less, 55 or less, 50 or less, 45 or less, 40 or less, 35 or less, or 30 or less); optionally but preferably, the average degree of polymerization of the brush arm and / or the sum of m+n may also be at least 8 (e.g., at least 11, at least 14, at least 17, at least 20, at least 23 or at least 25) (in particular, the average degree of polymerization of the brush arm and / or the sum of m+n may be 75 or less, 60 or less, 11 to 75, or 14 to 60). Further, or alternatively, the brush arm can be characterized by a ratio of m:n; for example, the ratio of m:n can be 1:99 to 9:1, 1:49 to 4:1, 1:25 to 2:1, 1:19 to 1.5:1, 1:14 to 1:1, or 1:9 to 1:1.5 (in particular, 1:25 to 2:1, 1:19 to 1.5:1, 1:14 to 1:1, or 1:9 to 1:1.5).

[0031] The copolymer backbone may comprise, consist essentially of, or consist of repeating units of at least two different acrylate monomers of formulas (3) and (4), respectively.

[0032]

[0033] In equations (3) and (4), each R 1 and R 3 It can be independently a hydrogen, linear or branched C1-C4 alkyl moiety or a mixture thereof (particularly hydrogen, methyl and / or ethyl); each R 2 It can be independently a covalently linked copolymer brush arm, residual hydrogen, residual trisubstituted silyl group (wherein each substituent is independently a linear, branched, and / or cyclic C1-C8 alkyl, aryl, alkylaryl, or aralkyl structural moiety), residual linear, cyclic, or branched C1-C7 acyl structural moiety, residual linear or branched C1-C4 hydroxyalkyl structural moiety, or residual monovalent counterion (especially covalently linked copolymer brush arms, residual hydrogen, residual linear or branched C2-C4 hydroxyalkyl structural moiety, or residual monovalent counterion); and each R 4 It can be independently linear, branched, and / or cyclic C8-C 30 Alkyl, aryl, alkylaryl, or aralkyl structural moieties (especially linear or branched C8-C) 22 (alkyl structure moiety). In a particular embodiment, the brush copolymer composition comprises a copolymer backbone wherein at least 40 mol% (e.g., at least 45 mol%, at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 65 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, or at least 90 mol%) of R2 The groups are covalently linked copolymer brush arms. In one particular embodiment, it is believed that the copolymer backbone may be a random (or near-random) copolymer, but in any case not a block copolymer, and generally does not have high block copolymer characteristics.

[0034] When a residual monovalent counterion is present, it can advantageously be a monovalent cation. In some embodiments, the residual monovalent counterion may comprise, consist essentially of, or consist of: metal ions such as lithium, potassium, sodium, copper(I), silver(I), etc., or combinations thereof; nonmetal ions such as ammonium, etc.; or mixtures thereof.

[0035] In embodiments where the copolymer backbone consists only of monomers of formulas (1) and (2), the sum of subscripts a and b naturally represents 100 mol% of the average degree of polymerization of the copolymer backbone. However, in embodiments where the copolymer backbone comprises or is substantially composed of monomers of formulas (1) and (2), the sum of a+b may be 60 mol% to 100 mol% of the average degree of polymerization of the copolymer backbone (e.g., 60 mol% to 99 mol%, 60 mol% to 95 mol%, 60 mol% to 90 mol%, 60 mol% to 85 mol%, 60 mol% to 80 mol%, 70 mol% to 100 mol%, 70 mol% to 99 mol%, 70 mol% to 95 mol%, 70 mol% to 90 mol%, 70 mol% to 8 ... 5 mol%, 70 mol% to 80 mol%, 80 mol% to 100 mol%, 80 mol% to 99 mol%, 80 mol% to 95 mol%, 80 mol% to 90 mol%, 90 mol% to 100 mol%, 90 mol% to 99 mol%, 90 mol% to 95 mol%, 95 mol% to 100 mol%, 95 mol% to 99 mol%, or 99 mol% to 100 mol%; particularly 90 mol% to 100 mol%, 95 mol% to 100 mol%, or 99 mol% to 100 mol%.

[0036] Additionally or alternatively, the average degree of polymerization of the copolymer backbone and / or the sum of a+b may be 500 or less (e.g., 450 or less, 400 or less, 350 or less, 300 or less, 250 or less, 200 or less, 150 or less, 120 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, or 50 or less); optionally but preferably, the average degree of polymerization of the copolymer backbone and / or the sum of a+b may also be at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 75 or at least 100 (in particular, the average degree of polymerization of the copolymer backbone and / or the sum of a+b may be 400 or less, 250 or less, 20 to 250, or 25 to 200). Further, or alternatively, the copolymer backbone can be characterized by the ratio of the subscript a:b; for example, the ratio of a:b can be 1:19 to 1:1.5, 1:14 to 1:2, 1:9 to 1:2.5, 1:7 to 1:3, 1:6 to 1:3.5 or about 1:4 (in particular, 1:19 to 1:1.5, 1:7 to 1:3, or 1:6 to 1:3.5).

[0037] Brush copolymer compositions and their reactants / intermediates can be manufactured by many different methods. Specific methods and materials are disclosed herein. However, other methods and / or materials can be used to obtain the same or similar brush copolymer composition products.

[0038] For example, copolymer brush arms can be manufactured by polymerizing at least two different cyclic monomers, which form repeating units of formulas (1) and (2) respectively during polymerization. Examples of such monomers may include, but are not necessarily limited to, 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-propenyl-2-oxazoline, 2-butyl-2-oxazoline, 2-(methylpropyl)-2-oxazoline, 2-tert-butyl-2-oxazoline, 2-butenyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-(methylbutyl)-2-oxazoline, 2-(dimethylpropyl)-2-oxazoline, 2-pentenyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-(methylpentyl)-2-oxazoline, 2-(dimethylbutyl)-2-oxazoline, 2-(ethylbutyl)-2-oxazoline, 2-(methylpentyl)-2-oxazoline, 2-(dimethylbutyl)-2-oxazoline, 2-(ethylbutyl)-2-oxazoline, 2-(methylpropyl ...methylpropyl)-2-oxazoline, 2-(methylpropyl)-2-oxazoline, 2-(methylpropyl)-2-oxazoline, 2-(methylpropyl)- 2-Hexenyl-2-oxazoline, 2-Hexadienyl-2-oxazoline, 2-Heptyl-2-oxazoline, 2-(Methylhexyl)-2-oxazoline, 2-(Dimethylpentyl)-2-oxazoline, 2-(Ethylpentyl)-2-oxazoline, 2-Heptenyl-2-oxazoline, 2-Heptadienyl-2-oxazoline, 2-Octyl-2-oxazoline, 2-Nonyl-2-oxazoline, 2-Decyl-2-oxazoline, 2-Undecyl-2-oxazoline, 2-Dodecyl-2-oxazoline, 2-Tetrazyl-2-oxazoline, 2-Tetradecyl-2-oxazoline, 2-Pentadecanyl-2-oxazoline, 2-Pentadecanyl-2-oxazoline, 2-Hexadecyl- 2-Oxazoline, 2-Heptadecanyl-2-oxazoline, 2-(Methylhexadecyl)-2-oxazoline, 2-Heptadecanyl-2-oxazoline, 2-Heptadecanyl-2-oxazoline, 2-Heptadecanyl-2-oxazoline, 2-Heptadecanyl-2-oxazoline, 2-Octadecanyl-2-oxazoline, 2-Nondecyl-2-oxazoline, 2-Nondecyl-2-oxazoline, 2-Ninedecyl-2-oxazoline, 2-Ninedecyl-2-oxazoline, 2-Ninedecyl-2-oxazoline, 2-Ninedecyl-2-oxazoline, 2-Ninedecyl-2-oxazoline, 2-Eicosyl-2-oxazoline, 2-Eicosyl-2-oxazoline, 2-Eicosyl-2-oxazoline 2-Tridecyl-2-oxazoline, 2-Tetradecyl-2-oxazoline, 4,5-dihydro-1,3-oxazine, 2-Methyl-4,5-dihydro-1,3-oxazine, 2-Ethyl-4,5-dihydro-1,3-oxazine, 2-Propyl-4,5-dihydro-1,3-oxazine, 2-Isopropyl-4,5-dihydro-1,3-oxazine, 2-Propylene-4,5-dihydro-1,3-oxazine, 2-Butyl-4,5-dihydro-1,3-oxazine, 2-(Methylpropyl)-4,5-dihydro-1,3-oxazine, 2-tert-Butyl-4,5-dihydro-1,3-oxazine, 2-Butenyl-4,5-dihydro-1,3-oxazine, 2-Pentyl-4,5-dihydro-1,3-oxazine3-Oxazine, 2-(methylbutyl)-4,5-dihydro-1,3-oxazine, 2-(dimethylpropyl)-4,5-dihydro-1,3-oxazine, 2-pentenyl-4,5-dihydro-1,3-oxazine, 2-hexyl-4,5-dihydro-1,3-oxazine, 2-(methylpentenyl)-4,5-dihydro-1,3-oxazine, 2-(dimethylbutyl)-4,5-dihydro-1,3-oxazine, 2-(ethylbutyl)-4,5-dihydro-1,3-oxazine, 2-hexenyl-4,5-dihydro-1,3-oxazine, 2-hexadienyl-4,5-dihydro-1,3-oxazine, 2-heptyl-4,5-dihydro-1,3-oxazine, 2-heptyl-4,5-dihydro-1,3-oxazine, 2-heptyl-4,5-dihydro-1,3-oxazine, 2-heptyl-4,5-dihydro-1,3-oxazine, 2-(methylhexyl)-4,5-dihydro-1,3-oxazine Hydrogen-1,3-oxazine, 2-(dimethylpentyl)-4,5-dihydro-1,3-oxazine, 2-(ethylpentyl)-4,5-dihydro-1,3-oxazine, 2-heptenyl-4,5-dihydro-1,3-oxazine, 2-heptadienyl-4,5-dihydro-1,3-oxazine, 2-octyl-4,5-dihydro-1,3-oxazine, 2-nonyl-4,5-dihydro-1,3-oxazine, 2-decyl-4,5-dihydro-1,3-oxazine, 2-undecyl-4,5-dihydro-1,3-oxazine, 2-dodecyl-4,5-dihydro-1,3-oxazine, 2-tridecyl-4,5-dihydro-1,3-oxazine, 2-tetradecyl-4,5-dihydro-1,3- Oxazine, 2-pentadecanyl-4,5-dihydro-1,3-oxazine, 2-pentadenyl-4,5-dihydro-1,3-oxazine, 2-hexadecyl-4,5-dihydro-1,3-oxazine, 2-heptadecyl-4,5-dihydro-1,3-oxazine, 2-(methylhexadecyl)-4,5-dihydro-1,3-oxazine, 2-heptadecenyl-4,5-dihydro-1,3-oxazine, 2-heptadecadienyl-4,5-dihydro-1,3-oxazine, 2-heptadectrienyl-4,5-dihydro-1,3-oxazine, 2-heptadecanetetraenyl-4,5-dihydro-1,3-oxazine, 2-octadecyl-4,5-dihydro-1,3-oxazine, 2-nonadecanyl-4,5-dioxazine Hydrogen-1,3-oxazine, 2-nonadenyl-4,5-dihydro-1,3-oxazine, 2-nonadecanedenyl-4,5-dihydro-1,3-oxazine, 2-nonadecanedenyl-4,5-dihydro-1,3-oxazine, 2-nonadecanedenyl-4,5-dihydro-1,3-oxazine, 2-nonadecanedenyl-4,5-dihydro-1,3-oxazine, 2-eicosyl-4,5-dihydro-1,3-oxazine, 2-monodecyl-4,5-dihydro-1,3-oxazine, 2-monodecyl-4,5-dihydro-1,3-oxazine, 2-monodecyl-4,5-dihydro-1,3-oxazine, 2-monodecyl-4,5-dihydro-1,3-oxazine, 2-monodecyl-4,5-dihydro-1,3-oxazine, and combinations thereof.

[0039] In the case of copolymerization of at least two different (hetero)cyclic monomers (e.g., oxazoline and / or oxazine as described herein, each containing nitrogen and oxygen atoms), the brush arm can be advantageously formed using cationic ring-opening polymerization (CROP). Although radical polymerization, anionic polymerization, or other polymerization schemes do not preclude the use of (hetero)cyclic monomers such as oxazoline / oxazine, the cationic method can achieve relatively stable oxazoline-onium / oxazine-onium (hetero)cyclic cationic compounds at polymerizable chain ends. As will be understood by those skilled in the art, suitable CROP initiators may include, but are not necessarily limited to, electrophilic sulfonates such as alkyl toluenesulfonates (e.g., methyl toluenesulfonate), alkyl nosylates, alkyl brosylates, alkyl triflates, etc., oxazine-onium salts, oxazoline-onium salts, alkyl halides, Lewis acids containing relatively stable anions, and other functional compounds with sufficiently low (e.g., essentially none) nucleophilic properties, as well as combinations or mixtures thereof. The appropriate (co)polymerization temperature can be selected based on the choice of monomers and initiators, for example, to achieve relatively efficient initiation / proliferation while reducing or eliminating undesirable termination reactions and / or side reactions.

[0040] Although suitable initiators can be diluted with appropriate solvents, CROP polymerization can advantageously be carried out in relatively low concentrations of solvent, such as in bulk (any small amount of initiator solvent added to the monomer reactant system is still considered "in bulk" here, as any initiator solvent typically represents only trace amounts relative to the amounts of the at least two monomers and any other polymerization reactants / promoters). In practice, living or pseudo-living polymerization processes are possible when the polymer chain-end structures are sufficiently stable, which generally allow for better control of molecular weight, molecular weight distribution, and reduced side reactions, thereby typically resulting in more uniform and chemically stable brush-like copolymer arms. Living or pseudo-living polymerization can further offer the advantage that copolymer brush arms can be grafted onto sites on the copolymer backbone with little or no activation or post-polymerization functionalization.

[0041] Alternatively, at least one (some) or both (all) monomers that polymerize to form the at least two different repeating units may be acyclic. In one such example, a single acyclic monomer may be used to polymerize an originally homopolymerized poly(alkyleneamine) chain (e.g., poly(ethyleneethyleneamine) or (poly(propyleneamine)), followed by a post-polymerization reaction to acylate the secondary amine of the main chain with at least two different acyl groups to form a copolymer brush arm having repeating units of formulas (1) and (2). In another such example, at least two different monomers (one / some or both / all of which may be acyclic) may be used to copolymerize an intermediate copolymer having alkyleneamine and / or functionalized alkyleneamine repeating units, followed by a post-polymerization reaction to one or two side groups on the main chain nitrogen of the respective repeating unit thus formed to selectively acylate these nitrogens with appropriate acyl groups to subsequently form a copolymer brush arm having repeating units of formulas (1) and (2).

[0042] In similar but still alternative embodiments, both (all) monomers that polymerize to form the at least two different repeating units may be cyclic to facilitate the ring-opening polymerization process; however, one (some) or both (all) monomers may be selected to form an intermediate polymer or copolymer in which one (some) or two (all) functional groups on the nitrogen atom of the main chain are different from R described in formulas (1) and (2). 5 -C(=O)- and R 6 -C(=O)-acyl group, after which one or two side groups on the main chain nitrogen of the corresponding repeating unit can be applied to the postpolymerization reaction to selectively acylate these nitrogens with appropriate acyl groups.

[0043] The copolymer backbone can be manufactured by polymerizing at least two different acrylate monomers, which, upon polymerization, will respectively form repeating units of formula (3) and (4). Examples of monomers that can polymerize to form repeating units of formula (3) may include, but are not limited to, acrylic acid, methacrylic acid, ethylacrylic acid, trimethylsilyl acrylate, trimethylsilyl methacrylate, ethyl dimethylsilyl acrylate, ethyl dimethylsilyl methacrylate, phenyl dimethylsilyl acrylate, phenyl dimethylsilyl methacrylate, methyl diphenylsilyl acrylate, methyl diphenylsilyl methacrylate, tolyl dimethylsilyl acrylate, tolyl dimethylsilyl methacrylate, benzyl dimethylsilyl acrylate, and benzyl dimethyl methacrylate. Silyl acrylate, Triphenylsilyl acrylate, Triphenylsilyl methacrylate, Acetic anhydride, Acetic anhydride, Acetic anhydride, Ethyl acrylate, Propionic anhydride, Propionic anhydride, Ethyl acrylate, Butyric anhydride, Methyl acrylate, Ethyl acrylate, Isobutyric anhydride, Isobutyric anhydride, Ethyl acrylate, Valeric anhydride, Valeric anhydride, Ethyl acrylate, Methylbutyric anhydride, Methylbutyric anhydride, Ethyl acrylate, Pteropenic anhydride, Pteropenic anhydride, Ethyl acrylate, Pteropenic anhydride Acrylic hexanoic anhydride, methacrylic hexanoic anhydride, ethylacrylic hexanoic anhydride, methylvaleric anhydride, methacrylic methylvaleric anhydride, ethylacrylic methylvaleric anhydride, dimethylbutyric anhydride, dimethylbutyric anhydride, ethylacrylic dimethylbutyric anhydride, heptanoic anhydride, methacrylic heptanoic anhydride, ethylacrylic heptanoic anhydride, methylacrylic hexanoic anhydride, methylacrylic hexanoic anhydride, ethylacrylic methylhexanoic anhydride, dimethylvaleric anhydride, dimethylvaleric anhydride, ethylacrylic dimethylvaleric anhydride, ethylvaleric anhydride, ethylacrylic ethylvaleric anhydride, cyclohexane acrylate Formic anhydride, cyclohexane methacrylate formic anhydride, cyclohexane ethyl methacrylate formic anhydride, benzoic acid anhydride, benzoic acid methacrylate, benzoic acid ethyl methacrylate, hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, lithium acrylate, lithium methacrylate, potassium acrylate, potassium methacrylate, sodium acrylate, sodium methacrylate, copper acrylate (I), copper methacrylate (I), silver acrylate (I), silver methacrylate (I), ammonium acrylate, ammonium methacrylate, alkylated (alkyl)ammonium acrylate (e.g.,Monomethylammonium acrylate, monomethylammonium methacrylate, dimethylammonium acrylate, dimethylammonium methacrylate, trimethylammonium acrylate, trimethylammonium methacrylate, tetramethylammonium acrylate, tetramethylammonium methacrylate, monoethylammonium acrylate, monoethylammonium methacrylate, diethylammonium acrylate, diethylammonium methacrylate, triethylammonium methacrylate, triethylammonium methacrylate, tetraethylammonium methacrylate, tetraethylammonium methacrylate, etc., or mixtures thereof, or combinations thereof.

[0044] Examples of monomers that can polymerize to form repeating units of formula (4) may include, but are not necessarily limited to, octyl acrylate, octyl methacrylate, methyl heptyl acrylate, methyl heptyl methacrylate, ethylhexyl methacrylate, dimethylhexyl acrylate, dimethylhexyl methacrylate, trimethylpentyl acrylate, trimethylpentyl methacrylate, methyl ethyl pentyl acrylate, methyl ethyl pentyl methacrylate, propyl pentyl acrylate, propyl pentyl methacrylate, cyclooctyl acrylate, cyclooctyl methacrylate, cycloheptamethyl acrylate, cycloheptamethyl methacrylate, tricyclo[3.3.0.0]octyl acrylate, tricyclo[3.3.0.0]octyl acrylate, tricyclo[2.2.1.1]octyl acrylate, methacrylic acid Tricyclo[2.2.1.1]octyl acrylate, Bicyclo[2.2.2]octyl acrylate, Bicyclo[2.2.2]octyl methacrylate, Bicyclo[3.2.1]octyl acrylate, Bicyclo[3.2.1]octyl methacrylate, Octahydrocyclopentadienyl acrylate, Octahydrocyclopentadienyl methacrylate, Methylcycloheptayl acrylate, Methylcycloheptayl methacrylate, Cycloheptayl acrylate, Cycloheptayl methacrylate, Cycloheptayl methacrylate, Cyclohexyl ethyl acrylate, Ethylcyclohexyl acrylate, Ethylcyclohexyl methacrylate, Dimethylcyclohexyl acrylate, Dimethylcyclohexyl methacrylate, Methylcyclohexyl acrylate, Methylcyclohexyl methacrylate, Cyclopentylpropyl acrylate Cyclopentyl methacrylate, propyl cyclopentyl acrylate, propyl cyclopentyl methacrylate, methyl cyclopentyl ethyl methacrylate, methyl cyclopentyl ethyl methacrylate, dimethyl cyclopentyl acrylate, dimethyl cyclopentyl methacrylate, ethyl cyclopentyl acrylate, ethyl cyclopentyl methacrylate, trimethyl cyclopentyl acrylate, trimethyl cyclopentyl methacrylate, methyl ethyl cyclopentyl acrylate, methyl ethyl cyclopentyl methacrylate, benzocyclopentadienyl acrylate, benzocyclopentadienyl methacrylate, methyl benzyl acrylate, methyl benzyl methacrylate, benzyl methyl methacrylate, benzyl methyl methacrylate, dimethyl phenyl acrylate, dimethyl phenyl methacrylate Ethyl phenyl acrylate, ethyl phenyl methacrylate, styrene acrylate, phenethyl methacrylate, nonyl acrylate, nonyl methacrylate, methyl octyl acrylate, methyl octyl methacrylate, ethyl heptayl acrylate, ethyl heptayl methacrylate, dimethyl heptayl acrylate, dimethyl heptayl methacrylate, trimethyl hexyl acrylate, trimethyl hexyl methacrylate, methyl ethyl hexyl acrylate, methyl ethyl hexyl methacrylate, propyl hexyl acrylate, propyl hexyl methacrylate, tetramethyl pentyl acrylate, tetramethyl pentyl methacrylate, ethyl dimethyl pentyl acrylate, ethyl dimethyl pentyl methacrylate, diethyl pentyl acrylate, diethyl pentyl methacrylateTricyclo[4.3.0.0]nonyl acrylate, Tricyclo[4.3.0.0]nonyl methacrylate, Bicyclo[3.2.2]nonyl acrylate, Bicyclo[3.2.2]nonyl methacrylate, Bicyclo[3.3.1]nonyl acrylate, Bicyclo[3.3.1]nonyl methacrylate, Bicyclo[4.2.1]nonyl acrylate, Bicyclo[4.2.1]nonyl methacrylate, Octahydroindene acrylate, Octahydroindene methacrylate, Cyclooctyl acrylate, Cyclooctyl methacrylate, Methylcyclooctyl acrylate, Methylcyclooctyl methacrylate, Octahydrocyclopentadienyl acrylate, Octahydrocyclopentadienyl methacrylate, Methyl octahydrocyclopentadienyl acrylate, Methyl Methyl octahydrocyclopentadienyl acrylate, ethyl cycloheptayl acrylate, ethyl cycloheptayl methacrylate, cycloheptayl ethyl acrylate, cycloheptayl ethyl methacrylate, dimethyl cycloheptayl acrylate, dimethyl cycloheptayl methacrylate, methyl cycloheptayl acrylate, methyl cycloheptayl methacrylate, cyclohexylpropyl acrylate, cyclohexylpropyl methacrylate, propyl cyclohexyl acrylate, propyl cyclohexyl methacrylate, methyl ethyl cyclohexyl acrylate, methyl cyclohexyl acrylate, methyl cyclohexyl ethyl methacrylate, methyl cyclohexyl methacrylate, ethyl cyclohexyl methyl methacrylate, ethyl cyclohexyl methacrylate, ethyl cyclohexyl acrylate, ethyl cyclohexyl methacrylate, trimethyl cyclohexyl acrylate, propylene Dimethyl cyclohexyl methyl acrylate, dimethyl cyclohexyl methyl methacrylate, cyclopentyl butyl acrylate, cyclopentyl butyl methacrylate, butyl cyclopentyl acrylate, butyl cyclopentyl methacrylate, methyl cyclopentyl propyl acrylate, methyl cyclopentyl propyl methacrylate, propyl cyclopentyl methyl acrylate, propyl cyclopentyl methyl methacrylate, diethyl cyclopropyl acrylate, diethyl cyclopentyl methacrylate, ethyl cyclopentyl acrylate, ethyl cyclopentyl methacrylate, dimethyl cyclopentyl acrylate, dimethyl cyclopentyl acrylate, tetramethyl cyclopentyl acrylate, tetramethyl cyclopentyl methacrylate, trimethyl cyclopentyl methyl acrylate, trimethyl cyclopentyl methyl methacrylate, indole acrylate, Indene methacrylate, spiro[4.4]nonyl acrylate, spiro[4.4]nonyl methacrylate, spiro[4.4]nonadienyl acrylate, spiro[4.4]nonadienyl methacrylate, spiro[4.4]nonatetraenyl acrylate, spiro[4.4]nonatetraenyl methacrylate, methyl phenyl ethyl methacrylate, methyl benzocyclopentadienyl acrylate, methyl benzocyclopentadienyl methacrylate, methyl benzocyclopentadienyl methacrylate, methyl benzocyclopentadienyl methacrylate, ethyl benzyl acrylate, ethyl benzyl methacrylate, benzyl ethyl methacrylate, benzyl ethyl methacrylate, dimethyl benzyl acrylate, dimethyl benzyl methacrylate, phenyl propyl acrylate, phenyl propyl methacrylatePropyl phenyl acrylate, propyl phenyl methacrylate, trimethyl phenyl acrylate, trimethyl phenyl methacrylate, methyl ethyl phenyl acrylate, methyl ethyl phenyl methacrylate, methyl phenyl ethyl acrylate, decyl acrylate, decyl methacrylate, methyl nonyl acrylate, methyl nonyl methacrylate, ethyl octyl acrylate, ethyl octyl methacrylate, dimethyl octyl acrylate, dimethyl octyl methacrylate, propyl heptayl acrylate, propyl heptayl methacrylate, methyl ethyl heptayl acrylate, methyl ethyl heptayl methacrylate, trimethyl heptayl methacrylate, butyl hexyl acrylate, butyl hexyl methacrylate, tetramethyl hexyl acrylate Tetramethylhexyl methacrylate, dimethyl ethylhexyl acrylate, dimethyl ethylhexyl methacrylate, diethylhexyl acrylate, diethylhexyl methacrylate, pentamethyl pentyl acrylate, pentamethyl pentyl methacrylate, ethyl trimethyl pentyl acrylate, ethyl trimethyl pentyl methacrylate, diethyl methyl pentyl acrylate, diethyl methyl pentyl methacrylate, butyl methyl pentyl acrylate, butyl methyl pentyl methacrylate, ethyl propyl pentyl acrylate, ethyl propyl pentyl methacrylate, dimethyl propyl pentyl acrylate, dimethyl propyl pentyl methacrylate, tetracyclo[4.2.1.1.0]decyl acrylate, tetracyclo[4.2.1.1.0]decyl acrylate alkyl acrylate, adamantyl acrylate, adamantyl methacrylate, decahydrocyclopentacyclopentadienyl acrylate, decahydrocyclopentacyclopentadienyl methacrylate, tricyclic acrylate [4.4.0.0]decyl acrylate, tricyclic methacrylate [4.4.0.0]decyl acrylate, tricyclic acrylate [4.2.1.1]decyl acrylate, tricyclic methacrylate [4.2.1.1]decyl acrylate, tricyclic acrylate [3.3.1.1]decyl acrylate, tricyclic methacrylate [3.3.1.1]decyl acrylate, tricyclic acrylate [2.2.2.2]decyl acrylate, tricyclic methacrylate [2.2.2.2]decyl acrylate, bicyclic acrylate [3.3.2]decyl acrylate, bicyclic methacrylate [3.3.2]decyl acrylate, bicyclic acrylate [4.4.0.0]decyl acrylate, tricyclic methacrylate [4.4.0.0]decyl acrylate, tricyclic acrylate [4.2.1.1]decyl acrylate, tricyclic methacrylate [4.2.1.1]decyl acrylate, tricyclic methacrylate [3.3.1.1]decyl acrylate, tricyclic methacrylate [3.3.2]decyl acrylate, bicyclic methacrylate [4.3.2]decyl acrylate, tri ... [4.2.2] Decyl ester, Bicyclo[4.2.2] Decyl ester, Decahydronaphthyl acrylate, Decahydronaphthyl methacrylate, Decahydroazyl acrylate, Decahydroazyl methacrylate, Methyl octahydroindene acrylate, Methyl octahydroindene methacrylate, Octahydroindene methyl acrylate, Octahydroindene methyl methacrylate, Octahydrocyclopentadienyl ethyl acrylate, Octahydrocyclopentadienyl ethyl methacrylate, Ethyl octahydrocyclopentadienyl acrylate, Ethyl octahydrocyclopentadienyl methacrylate, Methyl octahydrocyclopentadienyl methacrylate, Methyl octahydrocyclopentadienyl methacrylate, Dimethyl octahydrocyclopentadienyl acrylate, Dimethyl octahydrocyclopentadienyl methacrylateDimethyl cyclooctyl acrylate, Dimethyl cyclooctyl methacrylate, Methyl cyclooctyl methacrylate, Methyl cyclooctyl methacrylate, Ethyl cyclooctyl acrylate, Ethyl cyclooctyl methacrylate, Propyl cycloheptyl acrylate, Propyl cycloheptyl methacrylate, Propyl cycloheptyl methacrylate, Propyl cycloheptyl methacrylate, Propyl cycloheptyl methacrylate, Ethyl cycloheptyl methacrylate, Ethyl cycloheptyl methacrylate, Methyl cycloheptyl methacrylate, Ethyl cycloheptyl methacrylate, Propyl cycloheptyl methacrylate, Propyl cycloheptyl methacrylate, Trimethyl cycloheptyl acrylate, Trimethyl cycloheptyl methacrylate, Dimethyl cycloheptyl methacrylate, Dimethyl cycloheptyl methacrylate, Propyl cycloheptyl methacrylate, Cyclohexyl butyl acrylate, Cyclohexyl butyl methacrylate, Butyl cyclohexyl acrylate Butyl cyclohexyl methacrylate, propyl cyclohexyl methyl methacrylate, propyl cyclohexyl methyl methacrylate, methyl propyl cyclohexyl methacrylate, methyl cyclohexyl propyl methacrylate, methyl cyclohexyl propyl methacrylate, ethyl cyclohexyl ethyl methacrylate, ethyl cyclohexyl ethyl methacrylate, diethyl cyclohexyl acrylate, diethyl cyclohexyl methacrylate, dimethyl cyclohexyl ethyl methacrylate, dimethyl cyclohexyl methacrylate, tetramethyl cyclohexyl acrylate, tetramethyl cyclohexyl methacrylate, trimethyl cyclohexyl methyl methacrylate, trimethyl cyclohexyl methyl methacrylate, naphthyl acrylate, naphthyl methacrylate, tetrahydronaphthyl acrylate, methacrylic acid Tetrahydronaphthyl ester, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, azuleyl acrylate, azuleyl methacrylate, dimethylcyclopentadienyl acrylate, dimethylcyclopentadienyl methacrylate, methylcyclopentadienyl methacrylate, methylcyclopentadienyl methacrylate, ethylcyclopentadienyl acrylate, ethylcyclopentadienyl methacrylate, ethylcyclopentadienyl acrylate, ethylcyclopentadienyl methacrylate, spiro[4.5]decyl acrylate, spiro[4.5]decyl methacrylate, spiro[4.5]decadienyl acrylate, spiro[4.5]decadienyl methacrylate, spiro[4.5]decatetraenyl acrylate, spiro[4.5]decatetraenyl methacrylate .5] Decatralenyl acrylate, Butylphenyl acrylate, Butylphenyl methacrylate, Phenylbutyl acrylate, Phenylbutyl methacrylate, Propylbenzyl acrylate, Propylbenzyl methacrylate, Benzylpropyl acrylate, Trimethylbenzyl acrylate, Trimethylbenzyl methacrylate, Methylethylbenzyl acrylate, Methylethylbenzyl methacrylate, Methylphenylpropyl acrylate, Methylphenylpropyl methacrylate, Dimethylphenylethyl acrylate, Dimethylphenylethyl methacrylate, Ethylphenylethyl acrylate, Ethylphenylethyl methacrylate, Undecyl acrylate, Undecyl methacrylate, Methyldecyl acrylate, Methyldecyl methacrylateEthyl nonyl acrylate, ethyl nonyl methacrylate, dimethyl nonyl acrylate, dimethyl nonyl methacrylate, propyl octyl acrylate, propyl octyl methacrylate, methyl ethyl octyl acrylate, methyl ethyl octyl methacrylate, trimethyl octyl acrylate, trimethyl octyl methacrylate, butyl heptyl acrylate, butyl heptyl methacrylate, methyl propyl heptyl acrylate, methyl propyl heptyl methacrylate, diethyl heptyl acrylate, diethyl heptyl methacrylate, tetramethyl heptyl acrylate, tetramethyl heptyl methacrylate, pentyl hexyl acrylate, pentyl hexyl methacrylate, pentamethyl hexyl methacrylate, trimethyl ethyl acrylate methyl hexyl ester, trimethyl ethyl hexyl methacrylate, methyl diethyl hexyl acrylate, methyl diethyl hexyl methacrylate, propyl ethyl hexyl acrylate, propyl ethyl hexyl methacrylate, propyl dimethyl hexyl acrylate, propyl dimethyl hexyl methacrylate, tetracyclo[3.3.1.1.1]undecyl acrylate, tetracyclo[3.3.1.1.1]undecyl acrylate, tetracyclo[6.2.1.0.0]undecyl acrylate, tetracyclo[6.2.1.0.0]undecyl acrylate, tetracyclo[5.3.1.0.0]undecyl acrylate, tetracyclo[5.3.1.0.0]undecyl acrylate, methyl adamantyl acrylate, methyl Methyl adamantyl acrylate, adamantyl methyl acrylate, adamantyl methyl methacrylate, tricyclic [5.2.1.1]undecyl acrylate, tricyclic [5.2.1.1]undecyl methacrylate, tricyclic [4.3.1.1]undecyl acrylate, tricyclic [4.3.1.1]undecyl methacrylate, tricyclic [4.2.2.1]undecyl acrylate, tricyclic [4.2.2.1]undecyl methacrylate, tricyclic [3.3.2.1]undecyl acrylate, tricyclic [3.3.2.1]undecyl methacrylate, tricyclic [3.2.2.2]undecyl methacrylate, tricyclic [3.2.2.2]undecyl methacrylate Bicyclic [4.3.2]undecyl acrylate, Bicyclic [4.3.2]undecyl methacrylate, Bicyclic [4.4.1]undecyl acrylate, Bicyclic [4.4.1]undecyl methacrylate, Bicyclic [3.3.3]undecyl acrylate, Bicyclic [3.3.3]undecyl methacrylate, Bicyclic [5.3.1]undecyl acrylate, Bicyclic [5.3.1]undecyl methacrylate, Bicyclic [5.2.2]undecyl acrylate, Bicyclic [5.2.2]undecyl methacrylate, Bicyclic [6.2.1]undecyl acrylate, Bicyclic [6.2.1]undecyl methacrylate, Bicyclic [7.1.1]undecyl acrylateBicyclo[7.1.1]undecyl methacrylate, methyl decahydronaphthyl acrylate, methyl decahydronaphthyl methacrylate, decahydronaphthyl methacrylate, decahydronaphthyl methacrylate, methyl decahydroazolyl methacrylate, methyl decahydroazolyl methacrylate, decahydroazolyl methacrylate, decahydroazolyl methacrylate, dimethyl octahydroindole acrylate, dimethyl octahydroindole methacrylate, ethyl octahydroindole acrylate, ethyl octahydroindole methacrylate, ethyl octahydroindole acrylate, octahydroindole ethyl methacrylate, octahydrocyclopentadienylpropyl methacrylate, octahydrocyclopentadienylpropyl methacrylate, propyl octahydrocyclopentadienyl methacrylate, propyl octahydrocyclopentadienyl methacrylate Pentyl ester, Trimethylcyclooctyl acrylate, Trimethylcyclooctyl methacrylate, Dimethylcyclooctyl methacrylate, Dimethylcyclooctyl methacrylate, Ethylcyclooctyl methacrylate, Ethylcyclooctyl methacrylate, Butylcycloheptyl acrylate, Butylcycloheptyl methacrylate, Cycloheptyl methacrylate, Cycloheptyl methacrylate, Diethylcycloheptyl acrylate, Diethylcycloheptyl methacrylate, Tetramethylcycloheptyl acrylate, Tetramethylcycloheptyl methacrylate, Cyclohexylpentyl acrylate, Cyclohexylpentyl methacrylate, Pentylcyclohexyl methacrylate, Pentylcyclohexyl acrylate, Cyclohexyl acrylate Cyclopentadienyl acrylate, cyclopentadienyl acrylate, cyclopentadienyl phenyl acrylate, cyclopentadienyl phenyl methacrylate, phenylcyclopentadienyl acrylate, phenylcyclopentadienyl methacrylate, spiro[4.6]undecyl acrylate, spiro[4.6]undecyl acrylate, spiro[4.6]undecadienyl acrylate, spiro[4.6]undectrienyl acrylate, spiro[4.6]undectrienyl acrylate, spiro[4.6]undecpentenyl acrylate, spiro[4.6]undecpentenyl acrylate, methylnaphthyl acrylate, methylnaphthyl methacrylate, naphthyl methyl acrylate, methacrylic acid Naphthyl methyl ester, methyl dicyclopentadienyl acrylate, methyl dicyclopentadienyl methacrylate, methyl azuleyl acrylate, methyl azuleyl methacrylate, azuleyl methyl acrylate, azuleyl methyl methacrylate, methyl tetrahydronaphthyl acrylate, methyl tetrahydronaphthyl methacrylate, spiro[5.5]undecyl acrylate, spiro[5.5]undecyl methacrylate, diethyl benzyl acrylate, diethyl benzyl methacrylate, pentamethyl phenyl acrylate, pentamethyl phenyl methacrylate, phenyl pentyl acrylate, phenyl pentyl methacrylate, phenyl pentyl methacrylate, dodecyl acrylate, dodecyl methacrylate, methyl undecyl acrylate, methyl undecyl methacrylate, ethyl decyl acrylate,Ethyl decyl methacrylate, dimethyl decyl acrylate, dimethyl decyl methacrylate, propyl nonyl acrylate, propyl nonyl methacrylate, methyl ethyl nonyl acrylate, methyl ethyl nonyl methacrylate, trimethyl nonyl acrylate, trimethyl nonyl methacrylate, butyl octyl acrylate, butyl octyl methacrylate, methyl propyl octyl acrylate, methyl propyl octyl methacrylate, diethyl octyl acrylate, diethyl octyl methacrylate, tetramethyl octyl acrylate, tetramethyl octyl methacrylate, pentyl heptyl acrylate, pentyl heptyl methacrylate, pentamethyl heptyl acrylate, pentamethyl heptyl methacrylate, trimethyl ethyl heptyl acrylate, trimethyl Ethyl heptyl acrylate, methyl diethyl heptyl acrylate, methyl diethyl heptyl methacrylate, propyl ethyl heptyl acrylate, propyl ethyl heptyl methacrylate, propyl dimethyl heptyl acrylate, propyl dimethyl heptyl methacrylate, tetracyclo[7.2.1.0.0] dodecyl acrylate, tetracyclo[7.2.1.0.0] dodecyl acrylate, tetracyclo[4.2.2.1.1] dodecyl acrylate, tetracyclo[4.2.2.1.1] dodecyl acrylate, tetracyclo[4.3.1.1.1] dodecyl acrylate, tetracyclo[4.3.1.1.1] dodecyl acrylate, tetracyclo[3.3.2.1.1] dodecyl acrylate, tetracyclo[4.3.1.1.1] dodecyl acrylate, tetracyclo[4.3.1.1.1] dodecyl acrylate, tetracyclo[4.3.2.1.1] dodecyl acrylate [3.3.2.1.1] Dodecyl acrylate, ethyl adamantyl acrylate, ethyl adamantyl methacrylate, dimethyl adamantyl acrylate, dimethyl adamantyl methacrylate, adamantyl ethyl acrylate, adamantyl ethyl methacrylate, tricyclic acrylate [6.2.1.1] dodecyl acrylate, tricyclic methacrylate [6.2.1.1] dodecyl acrylate, tricyclic acrylate [5.3.1.1] dodecyl acrylate, tricyclic methacrylate [5.3.1.1] dodecyl acrylate, tricyclic acrylate [4.4.1.1] dodecyl acrylate, tricyclic methacrylate [4.4.1.1] dodecyl acrylate, tricyclic acrylate [5.2.2.1] dodecyl acrylate, tricyclic methacrylate [5.2. 2.1] Dodecyl ester, Tricyclic acrylate [4.3.2.1] Dodecyl ester, Tricyclic methacrylate [4.3.2.1] Dodecyl ester, Tricyclic acrylate [4.2.2.2] Dodecyl ester, Tricyclic methacrylate [4.2.2.2] Dodecyl ester, Tricyclic acrylate [3.3.2.2] Dodecyl ester, Tricyclic methacrylate [3.3.2.2] Dodecyl ester, Bicyclic acrylate [4.3.3] Dodecyl ester, Bicyclic methacrylate [4.3.3] Dodecyl ester, Bicyclic acrylate [4.4.2] Dodecyl ester, Bicyclic methacrylate [4.4.2] Dodecyl ester, Bicyclic acrylate [5.4.1] Dodecyl ester, Bicyclic methacrylate [5.4.1] Dodecyl ester,Bicyclic acrylate [5.3.2] dodecyl acrylate, bicyclic methacrylate [5.3.2] dodecyl acrylate, bicyclic acrylate [6.2.2] dodecyl acrylate, bicyclic methacrylate [6.2.2] dodecyl acrylate, bicyclic acrylate [6.3.1] dodecyl acrylate, bicyclic methacrylate [6.3.1] dodecyl acrylate, bicyclic acrylate [7.2.1] dodecyl acrylate, bicyclic methacrylate [7.2.1] dodecyl acrylate, bicyclic acrylate [8.1]. 1] Dodecyl ester, Bicyclo[8.1.1] Dodecyl ester, Ethyl decahydronaphthyl acrylate, Ethyl decahydronaphthyl acrylate, Decahydronaphthyl ethyl acrylate, Decahydronaphthyl ethyl methacrylate, Ethyl decahydroazolyl acrylate, Ethyl decahydroazolyl methacrylate, Decahydroazolyl ethyl acrylate, Decahydroazolyl ethyl methacrylate, Trimethyl octahydroindene acrylate, Trimethyl octahydroindene methacrylate, Propyl octahydroindene acrylate, Methyl Propyl octahydroindene acrylate, octahydroindene propyl acrylate, octahydroindene propyl methacrylate, butyl octahydrocyclopentadienyl acrylate, butyl octahydrocyclopentadienyl methacrylate, tetramethylcyclooctyl acrylate, tetramethylcyclooctyl methacrylate, diethylcyclooctyl acrylate, diethylcyclooctyl methacrylate, pentylcycloheptyl acrylate, pentylcycloheptyl methacrylate, cycloheptylpentyl acrylate, cycloheptylpentyl methacrylate, acrylic acid Pentamethylcycloheptayl ester, pentamethylcycloheptayl methacrylate, cyclohexylhexyl acrylate, cyclohexylhexyl methacrylate, cyclohexylhexyl acrylate, cyclohexylhexyl methacrylate, pentamethylcyclohexyl methyl acrylate, pentamethylcyclohexyl methyl methacrylate, acenaphthenic acrylate, acenaphthenic acrylate, acenaphthenic acrylate, acenaphthenic acrylate, biphenyl acrylate, biphenyl methacrylate, indacenyl acrylate acrylate), methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl cyclopentadienylcycloheptatrienyl acrylate, methyl cyclopentadienyl methacrylate, methyl cyclopentadienyl methacrylate, methyl cyclopentadienyl methacrylate, methyl cyclopentadienyl methacrylate, methyl cyclopentadienyl methacrylate, methyl cyclopentadienyl methacrylate, methyl cyclopentadienyl methacrylate Alkenylphenyl ester, cyclopentadienyl toluene acrylate, cyclopentadienyl toluene methacrylate, cyclopentadienyl benzyl acrylate, cyclopentadienyl benzyl methacrylate, methylphenylcyclopentadienyl acrylate, methylphenylcyclopentadienyl methacrylate, toluene cyclopentadienyl acrylate, toluene cyclopentadienyl methacrylate, spiro[5.6]dodecyl acrylate, spiro[5.6]dodecyl acrylate, spiro[5.6]dodecanetrienyl acrylateSpiro[5.6]dodecanetrienyl methacrylate, dimethylnaphthyl acrylate, dimethylnaphthyl methacrylate, ethylnaphthyl acrylate, ethylnaphthyl methacrylate, naphthyl ethyl acrylate, naphthyl ethyl methacrylate, dimethyl azuleyl acrylate, dimethyl azuleyl methacrylate, ethyl azuleyl acrylate, ethyl azuleyl methacrylate, azuleyl ethyl methacrylate, dimethyl tetrahydronaphthyl acrylate, dimethyl tetrahydronaphthyl methacrylate, triethylphenyl acrylate, triethylphenyl methacrylate, phenylhexyl acrylate, phenylhexyl methacrylate, hexylphenyl acrylate, hexylphenyl methacrylate, cyclohexylphenyl acrylate, cyclohexylphenyl methacrylate Benzyl acrylate, phenylcyclohexyl acrylate, phenylcyclohexyl methacrylate, tridecyl acrylate, tridecyl methacrylate, methyl dodecyl acrylate, methyl dodecyl methacrylate, dimethyl undecyl acrylate, dimethyl undecyl methacrylate, ethyl undecyl acrylate, ethyl undecyl methacrylate, trimethyl decyl acrylate, trimethyl decyl methacrylate, methyl ethyl decyl acrylate, methyl ethyl decyl methacrylate, propyl decyl acrylate, propyl decyl methacrylate, diethyl nonyl acrylate, diethyl nonyl methacrylate, tetramethyl nonyl acrylate, tetramethyl nonyl methacrylate, butyl nonyl acrylate, butyl nonyl methacrylate, propylene Methylpropyl nonyl acrylate, methylpropyl nonyl methacrylate, pentyl octyl acrylate, pentyl octyl methacrylate, pentamethyl octyl acrylate, pentamethyl octyl methacrylate, trimethyl ethyl octyl acrylate, trimethyl ethyl octyl methacrylate, methyl diethyl octyl acrylate, methyl diethyl octyl methacrylate, propyl ethyl octyl acrylate, propyl dimethyl octyl acrylate, propyl dimethyl octyl methacrylate, triethyl heptayl acrylate, triethyl heptayl methacrylate, tetracyclo[6.3.2.0.0]tridecyl acrylate, tetracyclo[6.3.2.0.0]tridecyl methacrylate, tetracyclo[6.2.1.1.1]tridecyl acrylate Tridecyl acrylate, tetracyclo[6.2.1.1.1]tridecyl acrylate, tetracyclo[5.3.1.1.1]tridecyl acrylate, tetracyclo[5.3.1.1.1]tridecyl acrylate, tetracyclo[4.4.1.1.1]tridecyl acrylate, tetracyclo[4.4.1.1.1]tridecyl acrylate, tetracyclo[4.3.2.1.1]tridecyl acrylate, tetracyclo[4.3.2.1.1]tridecyl acrylate, tetracyclo[4.2.2.2.1]tridecyl acrylate, tetracyclo[4.2.2.2.1]tridecyl acrylate, propyltrimonium acrylate, propyltrimonium acrylate, trimethyladamantyl acrylateTrimethyladamantyl methacrylate, tricyclic [7.2.1.1]tridecyl acrylate, tricyclic [7.2.1.1]tridecyl methacrylate, tricyclic [6.3.1.1]tridecyl methacrylate, tricyclic [6.3.1.1]tridecyl methacrylate, tricyclic [6.2.2.1]tridecyl methacrylate, tricyclic [6.2.2.1]tridecyl methacrylate, tricyclic [5.4.1.1]tridecyl methacrylate, tricyclic [5.4.1.1]tridecyl methacrylate, tricyclic [5.3.2.1]tridecyl methacrylate, tricyclic [5.3.2.1]tridecyl methacrylate, tricyclic [5.2.2.2]tridecyl methacrylate, methyl methacrylate Tridecyl acrylate [5.2.2.2], Tridecyl acrylate [4.4.2.1], Tridecyl methacrylate [4.4.2.1], Tridecyl acrylate [4.3.3.1], Tridecyl methacrylate [4.3.3.1], Tridecyl acrylate [4.3.2.2], Tridecyl methacrylate [4.3.2.2], Dodecyl acrylate, Dodecyl methacrylate, Dodecyl phenatenyl acrylate, Dodecyl phenatenyl methacrylate, Dodecyl arunyl acrylate, Dodecyl arunyl methacrylate, Spiro[6.6]decahexenyl acrylate, Spiro[6.6]decahexenyl methacrylate C6-enyl ester, spiro[6.6]tridecyltrienyl acrylate, spiro[6.6]tridecyltrienyl methacrylate, spiro[6.6]tridecyl acrylate, spiro[6.6]tridecyl methacrylate, methyldodecylene acrylate, methyldodecylene methacrylate, methyldodecyl(s)indaryl acrylate, methyldodecyl(s)indaryl methacrylate, methyldodecyl[heptyl]-m-trienyl acrylate, methyldodecyl[heptyl]-m-trienyl methacrylate, bicyclo[4.4.3]tridecyl acrylate, bicyclo[4.4.3]tridecyl methacrylate, bicyclo[5.5.1]tridecyl acrylate, bicyclo[5.5.1]tridecyl methacrylate Bicyclic acrylate [5.4.2]tridecyl acrylate, bicyclic methacrylate [5.4.2]tridecyl acrylate, bicyclic acrylate [5.3.3]tridecyl acrylate, bicyclic methacrylate [5.3.3]tridecyl acrylate, bicyclic acrylate [6.3.2]tridecyl acrylate, bicyclic methacrylate [6.3.2]tridecyl acrylate, bicyclic acrylate [6.4.1]tridecyl acrylate, bicyclic methacrylate [6.4.1]tridecyl acrylate, bicyclic acrylate [7.2.2]tridecyl acrylate, bicyclic methacrylate [7.2.2]tridecyl acrylate, bicyclic acrylate [7.3.1]tridecyl acrylate, bicyclic methacrylate [7.3.1]tridecyl acrylate, bicyclic acrylate [8.2.1]tridecyl acrylateBicyclo[8.2.1]tridecyl methacrylate, propyl decahydronaphthyl acrylate, propyl decahydronaphthyl methacrylate, decahydronaphthyl propyl methacrylate, decahydronaphthyl propyl methacrylate, trimethyl decahydronaphthyl acrylate, trimethyl decahydronaphthyl methacrylate, propyl decahydroazolyl acrylate, propyl decahydroazolyl methacrylate, trimethyl decahydroazolyl methacrylate, trimethyl decahydroazolyl methacrylate, tetramethyl octahydroindole acrylate, tetramethyl octahydroindole methacrylate, butyl octahydroindole acrylate, butyl octahydroindole methacrylate, diethyl octahydroindole acrylate, diethyl octahydroindole methacrylate, pentyl octahydrocyclopentadienyl acrylate, pentyl octahydrocyclopentadienyl methacrylate Alkenyl ester, pentamethylcyclooctyl acrylate, pentamethylcyclooctyl methacrylate, hexylcycloheptyl acrylate, hexylcycloheptyl methacrylate, hexamethylcycloheptyl acrylate, hexamethylcycloheptyl methacrylate, cyclohexylheptyl acrylate, cyclohexylcycloheptyl methacrylate, cyclohexylcycloheptyl acrylate, cyclohexylcycloheptyl methacrylate, cyclohexylcycloheptyl acrylate, cyclohexylcycloheptyl methacrylate, fluorenyl acrylate, fluorenyl methacrylate, finaxyl acrylate, finaxyl methacrylate, arunenyl acrylate, arunenyl methacrylate, methyl acenaphthenic acrylate, methyl acenaphthenic acrylate, methyl acenaphthenic acrylate, methyl acenaphthenic acrylate Methyl acenaphthene methacrylate, methyl acenaphthene methacrylate, methyl acenaphthene methacrylate, methyl biphenyl methacrylate, methyl biphenyl methacrylate, methyl methyl acenaphthene methacrylate, ... Alkyl esters, methyl ethyl undecyl acrylate, methyl ethyl undecyl methacrylate, propyl undecyl acrylate, propyl undecyl methacrylate, diethyl decyl acrylate, diethyl decyl methacrylate, tetramethyl decyl acrylate, tetramethyl decyl methacrylate, butyl decyl acrylate, butyl decyl methacrylate, methyl propyl decyl acrylate, methyl propyl decyl methacrylate, pentyl nonyl acrylate, pentyl nonyl methacrylate, pentamethyl nonyl acrylate, pentamethyl nonyl methacrylate, trimethyl ethyl nonyl acrylate, trimethyl ethyl nonyl methacrylate, methyl diethyl nonyl acrylate, methyl diethyl nonyl methacrylate, propyl ethyl nonyl acrylate,Propyl ethyl nonyl methacrylate, propyl dimethyl nonyl acrylate, propyl dimethyl nonyl methacrylate, hexyl octyl acrylate, hexyl octyl methacrylate, triethyl octyl acrylate, triethyl octyl methacrylate, dipropyl octyl acrylate, dipropyl octyl methacrylate, hexamethyl octyl acrylate, hexamethyl octyl methacrylate, dimethyl diethyl octyl acrylate, dimethyl diethyl octyl methacrylate, butyl ethyl octyl acrylate, butyl ethyl octyl methacrylate, butyl dimethyl octyl acrylate, butyl dimethyl octyl methacrylate, tetracyclo[6.2.2.1.1]tetradecyl acrylate, tetracyclo[6.2.2.1.1]tetradecyl methacrylate Ester, tetracyclo[6.3.1.1.1]tetradecyl acrylate, tetracyclo[6.3.1.1.1]tetradecyl methacrylate, tetracyclo[5.4.1.1.1]tetradecyl acrylate, tetracyclo[5.4.1.1.1]tetradecyl methacrylate, tetracyclo[5.3.2.1.1]tetradecyl methacrylate, tetracyclo[5.3.2.1.1]tetradecyl acrylate, tetracyclo[4.4.2.1.1]tetradecyl acrylate, tetracyclo[5.2.2.2.1]tetradecyl methacrylate, tetracyclo[4.4.2.1.1]tetradecyl methacrylate, tetracyclo[4.4.2.1.1]tetradecyl acrylate, tetracyclo[4.4.2.1.1]tetradecyl acrylate Tetradecyl acrylate, tetracyclo[4.4.2.1.1]tetradecyl acrylate, tetracyclo[4.3.2.2.1]tetradecyl acrylate, tetracyclo[4.3.2.2.1]tetradecyl acrylate, tetracyclo[4.3.3.1.1]tetradecyl acrylate, tetradecyl acrylate, tetradecylhydrocyclopentaenacolyl acrylate, tetradecylhydrocyclopentaenacolyl acrylate, tetradecylhydrocyclopentaenacolyl acrylate, tetradecylhydrodicyclopentacyclopentadienyl acrylate, tetradecylhydrodicyclopentacyclopentadienyl acrylate, tetradecylhydroanthrayl acrylate, tetradecylhydroanthrayl acrylate, tetradecylhydrophenanthrene acrylate, methyl Tetrahydrophenanthrene acrylate, Tetrahydrocycloheptanaphthyl acrylate, Tetrahydrocycloheptanaphthyl methacrylate, Hexahydrocycloheptanaphthyl acrylate, Hexahydrocycloheptanaphthyl methacrylate, Tetradecahydrooctalenyl acrylate, Tetrahydrooctalenyl methacrylate, Hexahydrooctalenyl acrylate, Hexahydrooctalenyl methacrylate, Tricyclo[8.2.1.1]tetradecyl acrylate, Tricyclo[8.2.1.1]tetradecyl methacrylate, Tricyclo[7.3.1.1]tetradecyl acrylate, Tricyclo[7.3.1.1]tetradecyl methacrylate, Tricyclo[7.2.2.1]tetradecyl acrylateTricyclic methacrylate [7.2.2.1]tetradecyl ester, tricyclic methacrylate [6.4.1.1]tetradecyl ester, tricyclic methacrylate [6.4.1.1]tetradecyl ester, tricyclic methacrylate [6.3.2.1]tetradecyl ester, tricyclic methacrylate [6.3.2.1]tetradecyl ester, tricyclic methacrylate [6.2.2.2]tetradecyl ester, tricyclic methacrylate [5.5.1.1]tetradecyl ester, tricyclic methacrylate [5.5.1.1]tetradecyl ester, tricyclic methacrylate [5.4.2.1]tetradecyl ester, tricyclic methacrylate [5.4.2.1]tetradecyl ester, tricyclic methacrylate [5.3.3.1]tetradecyl ester Tetradecyl ester, Tricyclic methacrylate [5.3.3.1] Tetradecyl ester, Tricyclic methacrylate [5.3.2.2] Tetradecyl ester, Tricyclic methacrylate [5.3.2.2] Tetradecyl ester, Tricyclic methacrylate [4.4.2.2] Tetradecyl ester, Tricyclic methacrylate [4.4.2.2] Tetradecyl ester, Tricyclic methacrylate [4.4.3.1] Tetradecyl ester, Tricyclic methacrylate [4.4.3.1] Tetradecyl ester, Tricyclic methacrylate [4.3.3.2] Tetradecyl ester, Tricyclic methacrylate [4.3.3.2] Tetradecyl ester, Methyl dodecyl methacrylate, Methyl dodecyl methacrylate, Dodecyl methacrylate, Dodecyl fluorene methyl methacrylate Methyl dodecyl phenaenoyl acrylate, methyl dodecyl phenaenoyl methacrylate, methyl dodecyl phenaenoyl acrylate, methyl dodecyl phenaenoyl methacrylate, methyl dodecyl arbutinyl acrylate, butyl methacrylate, diethyl adamantyl acrylate, diethyl adamantyl methacrylate, tetramethyl adamantyl acrylate, ethyl dodecyl acenaphthenic acrylate, dimethyl dodecyl acenaphthenic acrylate, dimethyl dodecyl acenaphthenic acrylate, dimethyl dodecyl acenaphthenic acrylate Dodecyl acenaphthenic ester, ethyl dodecyl(s) ethyl methacrylate, ethyl dodecyl(s) ethyl methacrylate, dimethyl ...Bicyclic [6.3.3]tetradecyl methacrylate, bicyclic [6.4.2]tetradecyl methacrylate, bicyclic [6.4.2]tetradecyl methacrylate, bicyclic [6.5.1]tetradecyl methacrylate, bicyclic [6.5.1]tetradecyl methacrylate, bicyclic [7.3.2]tetradecyl methacrylate, bicyclic [7.3.2]tetradecyl methacrylate, bicyclic [7.4.1]tetradecyl methacrylate, bicyclic [8.2.2]tetradecyl methacrylate, bicyclic [8.2.2]tetradecyl methacrylate, bicyclic [8.3.1]tetradecyl methacrylate, methyl methacrylate Bicyclo[8.3.1]tetradecyl acrylate, Bicyclo[9.2.1]tetradecyl acrylate, Bicyclo[9.2.1]tetradecyl methacrylate, Butyl decahydronaphthyl acrylate, Butyl decahydronaphthyl methacrylate, Diethyl decahydronaphthyl acrylate, Diethyl decahydronaphthyl methacrylate, Tetramethyl decahydronaphthyl acrylate, Tetramethyl decahydronaphthyl methacrylate, Butyl decahydroazoyl acrylate, Butyl decahydroazoyl methacrylate, Diethyl decahydroazoyl acrylate, Diethyl decahydroazoyl methacrylate, Tetramethyl decahydroazoyl acrylate, Tetramethyl decahydroazoyl methacrylate, Amyl octahydroindole acrylate, Amyl octahydroindole methacrylate Hexyl octahydrocyclopentadienyl acrylate, hexyl octahydrocyclopentadienyl methacrylate, cyclohexyl octahydrocyclopentadienyl acrylate, cyclohexyl octahydrocyclopentadienyl methacrylate, hexamethylcyclooctyl acrylate, hexamethylcyclooctyl methacrylate, cyclohexylcyclooctyl acrylate, cyclohexylcyclooctyl methacrylate, heptylcycloheptyl acrylate, heptylcycloheptyl methacrylate, cycloheptylcycloheptyl methacrylate, cyclopentaenafenyl acrylate, cyclopentaenafenyl methacrylate, dicyclopentacyclopentadienyl acrylate, dicyclopentacyclopentadienyl methacrylate, anthracene acrylate, anthracene methacrylate, acrylic acid phenanthrene acrylate, phenanthrene methacrylate, cyclohepta-naphthyl acrylate, cyclohepta-naphthyl methacrylate, bibenzyl acrylate, bibenzyl methacrylate, styrene acrylate, styrene methacrylate, bicycloheptatrienyl acrylate, bicycloheptatrienyl methacrylate, octadalenyl acrylate, octadalenyl methacrylate, pentadecyl acrylate, pentadecyl methacrylate, cyclopentanyl acrylate, cyclopentanyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, pyrene acrylate, pyrene methacrylate, fluoranyl acrylate, fluoranyl methacrylate, aceanthrylenyl acrylate, aceanthrylenyl methacrylate, dicyclopenta-heptanetrienyl acrylate, dicyclopenta-heptanetrienyl methacrylate, indene-indene acrylate, indene-indene methacrylateCyclooctaindacenyl acrylate, cyclooctaindacenyl methacrylate, cycloheptanyl acrylate, cycloheptanyl methacrylate, phenylnaphthyl acrylate, phenylnaphthyl methacrylate, bicyclooctatetraenyl acrylate, bicyclooctatetraenyl methacrylate, heptadecanyl acrylate, heptadecanyl acrylate, methylhexadecyl acrylate, methylhexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, octadecyl acrylate, octadecyl trimenyl acrylate, cyclopentapyrene acrylate, cyclopentapyrene methacrylate, cyclopentaaceanthrylenyl acrylate, cyclopentaaceanthrylenyl methacrylate, azulenoindacenyl acrylate acrylate), azoxyl methacrylate anthraceneyl acrylate, dicycloheptanaphthyl acrylate, dicycloheptanaphthyl methacrylate, dicycloocta-cyclopentarenyl acrylate, dicycloocta-cyclopentarenyl methacrylate, tetraphenyl acrylate, tetraphenyl methacrylate, tetraphenyl acrylate, acrylic acid, methyl ester, methacrylic acid Triphenyl acrylate, Triphenyl methacrylate, Cycloheptanthyl acrylate, Cycloheptanthyl methacrylate, Azuroxyl acrylate, Azuroxyl methacrylate, Nonadecanyl acrylate, Nonadecanyl methacrylate, Eicosyl acrylate, Eicosyl methacrylate, Indofluorenyl acrylate, Indofluorenyl methacrylate, Dicycloheptaindacenyl acrylate Acrylate), dicyclohepta-methyl methacrylate, peryl acrylate, peryl methacrylate, cycloheptapyrene acrylate, cycloheptapyrene methacrylate, dibenzo[a]fluoranyl acrylate, dibenzo[a]fluoranyl methacrylate, heptaleno fluorenyl acrylate, heptaleno fluorenyl methacrylate, dicyclohepta-naphthyl acrylate, dicyclohepta-naphthyl methacrylate, naphthyl acrylate, naphthyl methacrylate, azoxyl acrylate, azoxyl methacrylate, docosahexadecyl acrylate, docosahexadecyl acrylate, azoxyl acrylate, azoxyl methacrylate, dodecyl acrylate, dodecyl methacrylate, pentaphenyl acrylate, pentaphenyl methacrylate, pentaphenyl acrylate Pentaphenyl methacrylate, succinic acrylate, succinic methacrylate, cycloheptazo[a]heptane ...

[0045] In particular, regarding the brush copolymer composition according to this disclosure: each R 5 It can be independently linear or branched C2-C 18 Alkyl structure portion; each R 6 It can be independently used for linear C8-C 20 Alkyl structure portion; each R 1 and R 3 It can be hydrogen or methyl independently; each R 2 It can be independently a covalently linked copolymer brush arm, residual hydrogen, or residual linear or branched C1-C4 hydroxyalkyl structural moiety; each R 4 It can be independently used for linear or branched C8-C 24 The alkyl structure part; and y and z can each be 1.

[0046] Specifically, regarding the brush copolymer composition according to this disclosure, it satisfies three or more of the following (e.g., four or more, five or more, six or more, seven or more, eight or more, or all; particularly, five or more, seven or more, or all): the number average molecular weight of the brush copolymer composition, determined by gel permeation chromatography (GPC) at ~40°C using tetrahydrofuran (THF) containing ~2% (v / v) TEA as eluent, is from 30,000 g / mol to 100,000 g / mol against a poly(methyl methacrylate) (PMMA) standard; each R 5 Independently linear or branched C2-C 18 Alkyl structure portion; each R 6 Independently for linear C8-C 20 Alkyl structure portion; each R 1 and R 3 Each R is independently hydrogen or methyl; 4 Independently linear or branched C8-C 24 Alkyl structure portion; and y and z are each 1; each R 2 Independently covalently linked copolymer brush arms, residual hydrogen or residual linear or branched C1-C4 hydroxyalkyl structural moieties, and at least 70 mol% R 2 The groups are covalently linked copolymer brush arms; the sum of m+n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arms; the m:n ratio is 1:25 to 2:1; the sum of a+b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer backbone; the a:b ratio is 1:14 to 1:2; the sum of a+b is 250 or less; and the sum of m+n is 75 or less.

[0047] In some embodiments, the copolymer backbone can be manufactured by reversible deactivation radical polymerization (RDRP), such as reversible addition fragmentation chain transfer (RAFT) polymerization. Radical initiators used in such methods may include, but are not limited to, peroxides, diazo compounds, and combinations and / or hybrids thereof. In RAFT polymerization, for example, the chain transfer agent may be used in conjunction with the radical initiator. Suitable chain transfer agents can be selected based on the (copolymer) monomer system to be polymerized, for example, as described in S. Perrier's "Raft Polymerization - A User's Guide," Macromolecules, 2017, 50, 7443-47 ("Perrier article"), the contents of which are incorporated herein by reference, and chain transfer agents may be selected to include, but are not limited to, thiocarbonylthio groups, such as aromatic substituted alkyl dithionates. RAFT conditions can also be selected based on the (co)monomer system to be polymerized, as described in the Perrier article. Such (co)polymerization can be carried out under standard pressure, reduced pressure, or increased pressure. The polymerization temperature can also be varied over a wide range. In particular, polymerization can typically be carried out at temperatures ranging from approximately -20°C to approximately 200°C, for example, from approximately 50°C to approximately 150°C or from approximately 70°C to approximately 130°C.

[0048] In some embodiments, the brush copolymer compositions and / or individual brush arm components of the brush copolymer compositions according to this specification can advantageously exhibit upper critical dissolution temperature (UCST) behavior at concentrations of ~5 mg / mL in Group III base oils having a kinematic viscosity (KV100) of ~4 cSt at ~100°C. Turbidity analysis using UV-Vis spectroscopy (e.g., by varying the temperature and monitoring a sensitive wavelength or wavelength group, such as at approximately 600 nm) can be used to indicate such UCST behavior. In such turbidity analysis, the transition temperature occurring at ~50% transmittance (indicating dissolution or other wavelength-specific absorption / scattering) can be measured, and preferably at least two heating and cooling cycles (within a reasonably selected temperature range that does not induce significant (co)polymer degradation) are performed, and only data from heating and / or cooling cycles other than the first are considered (e.g., to reduce, suppress, or erase any prior thermal or association history). The UV-Vis turbidity transition of the brush arm at a wavelength of ~600 nm can be reduced to below ~80.0 °C (e.g., below ~75.0 °C, below ~70.0 °C, below ~65.0 °C, below ~60.0 °C, below ~55.0 °C, below ~50.0 °C, below ~45.0 °C, below ~40.0 °C, below ~35.0 °C, or below ~30 °C) at a cooling rate of ~1 °C / min during a second or subsequent (e.g., second or third) cooling cycle. Additionally or alternatively, it can be equal to or higher than ~-40.0 °C, equal to or higher than ~-30.0 °C, equal to or higher than ~-20.0 °C, equal to or higher than ~-10.0 °C, equal to or higher than ~0.0 °C, equal to or higher than ~10.0 °C, equal to or higher than ~15.0 °C, or equal to or higher than ~10.0 °C. 20.0°C), and / or in the second or subsequent (e.g., the second or third) heating cycle at a heating rate of ~1°C / min, below ~85.0°C (e.g., below ~80.0°C, below ~75.0°C, below ~70.0°C, below ~65.0°C, below ~60.0°C, below ~55.0°C, below ~50.0°C, below ~45.0°C, below ~40.0°C, below ~35.0°C, or below ~30°C; additionally or alternatively, equal to or higher than ~-40.0°C, equal to or higher than ~-30.0°C, equal to or higher than ~-20.0°C, equal to or higher than ~-10.0°C, equal to or higher than ~0.0°C, equal to or higher than ~10.0°C, equal to or higher than ~15.0°C, or equal to or higher than ~20.0°C).

[0049] Additionally or alternatively, such UCST behavior may manifest as a major exothermic transition in a differential scanning calorimeter (DSC) at a cooling rate of ~1 °C / min during a second or subsequent (e.g., a second or third) cooling cycle having a peak centered below ~85.0 °C (e.g., below ~80.0 °C, below ~75.0 °C, below ~70.0 °C, below ~65.0 °C, below ~60.0 °C, below ~55.0 °C, below ~50.0 °C, below 45.0 °C, below ~40.0 °C, below ~35.0 °C, or below ~30 °C; additionally or alternatively, equal to or above ~-40.0 °C, equal to or above ~-30.0 °C, equal to or above ~-20.0 °C, equal to or above ~-10.0 °C, equal to or above ~0.0 °C, equal to or above ~10.0 °C, equal to or above ~15.0 °C, or equal to or above ~20.0 °C). In such DSC analyses, as in the turbidity analysis described herein, it is preferable to perform at least two (e.g., at least three) heating and cooling cycles (within a reasonably selected temperature range that does not induce significant (co)polymer degradation) and to consider only data from heating and / or cooling cycles other than the first (e.g., to reduce, suppress, or erase any prior thermal or association history). As used herein, a “major” exothermic transition may represent the largest peak (or set of peaks, if multiple peaks have significant overlap) in terms of peak area or peak height.

[0050] Specifically, the brush copolymer compositions, the copolymer backbone portion of the brush copolymer compositions, and / or the brush arm copolymer portions of the brush copolymer compositions according to this disclosure may have a polydispersity of less than 1.60 (e.g., 1.55 or less, 1.50 or less, 1.45 or less, 1.40 or less, 1.35 or less, 1.30 or less, 1.25, or 1.20 or less) as measured by gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing ~2% (v / v) triethylamine (TEA) as the eluent at ~40°C, compared with a poly(methyl methacrylate) (PMMA) standard. Additionally or alternatively, the number-average molecular weight of the brush copolymer composition, determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing ~2% (v / v) TEA as the eluent at ~40°C against a poly(methyl methacrylate) (PMMA) standard, can be from 30,000 g / mol to 125,000 g / mol (e.g., 30,000 g / mol to 110,000 g / mol, 30,000 g / mol to 100,000 g / mol, 30,000 g / mol to 90,000 g / mol). 00 g / mol, 30,000 g / mol to 80,000 g / mol, 30,000 g / mol to 75,000 g / mol, 30,000 g / mol to 70,000 g / mol, 30,000 g / mol to 65,000 g / mol, 30,000 g / mol to 60,000 g / mol, 40,000 g / mol to 125,000 g / mol, 40,000 g / mol to 110,000 g / mol, 40,000 g / mol to 1 00,000 g / mol, 40,000 g / mol to 90,000 g / mol, 40,000 g / mol to 80,000 g / mol, 40,000 g / mol to 75,000 g / mol, 40,000 g / mol to 70,000 g / mol, 40,000 g / mol to 65,000 g / mol, 45,000 g / mol to 125,000 g / mol, 45,000 g / mol to 110,000 g / mol, 45,000 g / mol 100,000 g / mol, 45,000 g / mol to 90,000 g / mol, 45,000 g / mol to 80,000 g / mol, 45,000 g / mol to 75,000 g / mol, or 45,000 g / mol to 70,000 g / mol; particularly 30,000 g / mol to 100,000 g / mol, 35,000 g / mol to 80,000 g / mol, or 40,000 g / mol to 75,000 g / mol).

[0051] The brush copolymers according to this disclosure advantageously exhibit relatively high oil solubility or oil dispersibility. As used herein, "oil solubility" means that a composition comprising at least 0.1% by weight, preferably at least 0.5% by weight, of a comb copolymer viscosity modifier and at least 80% by weight (preferably at least 85% by weight, at least 90% by weight, or the balance) of a lubricating oil base oil can be assembled relatively easily without the formation of a stable macroscopic phase. Oil solubility and / or oil dispersibility can depend particularly on the properties of the base oil and the copolymer chemistry.

[0052] In some preferred embodiments, the monomers of the copolymer backbone are selected such that the calculated solubility parameter of the resulting copolymer backbone product (before reaction with the brush arm) using a group contribution-based method (as described in R. Fedors, “A Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquids,” Polym. Eng. Sci., 14(2), February 1974, pp. 147-54) is at most 9.46 (cal / cm³). 3 ) 1 / 2 For example, a maximum of 9.45 (cal / cm³) 3 ) 1 / 2 Maximum 9.44 (cal / cm³) 3 ) 1 / 2 Maximum 9.43 (cal / cm³) 3 ) 1 / 2 Maximum 9.42 (cal / cm³) 3 ) 1 / 2 Maximum 9.41 (cal / cm³) 3 ) 1 / 2 Maximum 9.40 (cal / cm³) 3 ) 1 / 2 Maximum 9.38 (cal / cm³) 3 ) 1 / 2 Maximum 9.36 (cal / cm³) 3 ) 1 / 2 Maximum 9.34 (cal / cm³) 3 ) 1 / 2 8.00 to 9.46, 8.00 (cal / cm) 3 ) 1 / 2 Up to 9.46 (cal / cm) 3 ) 1 / 2 8.00 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 28.00 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 8.00 (cal / cm) 3 ) 1 / 2 Up to 9.43 (cal / cm) 3 ) 1 / 2 8.00 (cal / cm) 3 ) 1 / 2 Up to 9.42 (cal / cm) 3 ) 1 / 2 8.00 (cal / cm) 3 ) 1 / 2 Up to 9.41 (cal / cm) 3 ) 1 / 2 8.00 (cal / cm) 3 ) 1 / 2 Up to 9.40 (cal / cm) 3 ) 1 / 2 8.00 (cal / cm) 3 ) 1 / 2 Up to 9.38 (cal / cm) 3 ) 1 / 2 8.00 (cal / cm) 3 ) 1 / 2 Up to 9.36 (cal / cm) 3 ) 1 / 2 8.00 (cal / cm) 3 ) 1 / 2 Up to 9.34 (cal / cm) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.46 (cal / cm) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.43 (cal / cm) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.42 (cal / cm) 3 )1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.41 (cal / cm) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.40 (cal / cm) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.38 (cal / cm) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.36 (cal / cm) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2 Up to 9.34 (cal / cm) 3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.46 (cal / cm) 3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.43 (cal / cm) 3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.42 (cal / cm) 3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.41 (cal / cm) 3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.40 (cal / cm) 3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.38 (cal / cm)3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.36 (cal / cm) 3 ) 1 / 2 8.40 (cal / cm) 3 ) 1 / 2 Up to 9.34 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.46 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.43 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.42 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.41 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.40 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.38 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.36 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.34 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2Up to 9.46 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.43 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.42 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.41 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.40 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.38 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.36 (cal / cm) 3 ) 1 / 2 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.34 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 ) 1 / 2 Up to 9.46 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 )1 / 2 Up to 9.43 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 ) 1 / 2 Up to 9.42 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 ) 1 / 2 Up to 9.41 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 ) 1 / 2 Up to 9.40 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 ) 1 / 2 Up to 9.38 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 ) 1 / 2 Up to 9.36 (cal / cm) 3 ) 1 / 2 8.90 (cal / cm) 3 ) 1 / 2 Up to 9.34 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm) 3 ) 1 / 2 Up to 9.46 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm) 3 ) 1 / 2 Up to 9.43 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm) 3 ) 1 / 2 Up to 9.42 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm) 3 ) 1 / 2 Up to 9.41 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm)3 ) 1 / 2 Up to 9.40 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm) 3 ) 1 / 2 Up to 9.38 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm) 3 ) 1 / 2 Up to 9.36 (cal / cm) 3 ) 1 / 2 9.00 (cal / cm) 3 ) 1 / 2 Up to 9.34 (cal / cm) 3 ) 1 / 2 9.10 (cal / cm) 3 ) 1 / 2 Up to 9.46 (cal / cm) 3 ) 1 / 2 9.10 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 9.10 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 9.10 (cal / cm) 3 ) 1 / 2 Up to 9.43 (cal / cm) 3 ) 1 / 2 9.10 (cal / cm) 3 ) 1 / 2 Up to 9.42 (cal / cm) 3 ) 1 / 2 9.10 (cal / cm) 3 ) 1 / 2 Up to 9.41 (cal / cm) 3 ) 1 / 2 9.10 (cal / cm) 3 ) 1 / 2 Up to 9.40 (cal / cm) 3 ) 1 / 2 9.10 (cal / cm) 3 ) 1 / 2 Up to 9.38 (cal / cm) 3 ) 1 / 2 9.10 (cal / cm) 3 ) 1 / 2 Up to 9.36 (cal / cm) 3 ) 1 / 29.10 (cal / cm) 3 ) 1 / 2 Up to 9.34 (cal / cm) 3 ) 1 / 2 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.46 (cal / cm) 3 ) 1 / 2 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.43 (cal / cm) 3 ) 1 / 2 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.42 (cal / cm) 3 ) 1 / 2 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.41 (cal / cm) 3 ) 1 / 2 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.40 (cal / cm) 3 ) 1 / 2 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.38 (cal / cm) 3 ) 1 / 2 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.36 (cal / cm) 3 ) 1 / 2 or 9.20 (cal / cm) 3 ) 1 / 2 Up to 9.34 (cal / cm) 3 ) 1 / 2 Specifically, the calculated solubility parameter can be up to 9.46 (cal / cm³). 3 ) 1 / 2 Maximum 9.45 (cal / cm³) 3 ) 1 / 2 8.20 (cal / cm) 3 ) 1 / 2Up to 9.46 (cal / cm) 3 ) 1 / 2 8.60 (cal / cm) 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 or 8.80 (cal / cm) 3 ) 1 / 2 Up to 9.44 (cal / cm) 3 ) 1 / 2 In Fedors' article, the solubility parameter δ is approximated by calculation as: δ=[(Σ i Δe i ) / (Σ i Δυ i )] 1 / 2 , where Δe i The individual tabulated energy of vaporization represents the vaporization energy of each i-th component in each repeating unit, and Δυ i Individually tabulated molar volumes representing the i components of each repeating unit.

[0053] If used to modify viscosity, the brush copolymer can be combined with a lubricating composition (containing at least a lubricant base oil and optionally one or more functional lubricating composition components) to form, for example, a viscosity-modified mixture. Specifically, the brush copolymer can be combined with a lubricating oil base oil containing Class I, II, III, and / or Class IV diluents / base oils, particularly containing at least one Class II base oil and / or at least one Class III base oil, while optionally containing Class IV metallocene-based or non-metallocene-based base oils and / or Class V base oils. Optionally, lubricant additives may also be included (e.g., by means of a concentrated lubricant additive package containing a minor amount of lubricating oil base oil and one or more of antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, detergents, defoamers, extreme pressure additives, pour point depressants, and sealing swelling control agents; or blends or combinations of only one or more of the listed additives).

[0054] In some applications, the brush copolymer (unlike any viscosity improver concentrate, which may contain additional (co)polymer components and / or additional diluents but no other lubricant-based functional components) may be present in amounts from 0.2% to 15% by mass based on the total mass of the lubricating composition, for example, 0.2% to 12% by mass, 0.2% to 9.0% by mass, 0.2% to 8.0% by mass, 0.2% to 7.0% by mass, 0.2% to 6.0% by mass, 0.2% to 5.0% by mass, 0.2% to 4.0% by mass, 0.2% to 3.5% by mass, 0.2% to 3.0% by mass, 0.2% to 2.5% by mass, and 0.2% to 2.0% by mass. 0.4% by mass, 0.4% to 15% by mass, 0.4% to 12% by mass, 0.4% to 9.0% by mass, 0.4% to 8.0% by mass, 0.4% to 7.0% by mass, 0.4% to 6.0% by mass, 0.4% to 5.0% by mass, 0.4% to 4.0% by mass, 0.4% to 3.5% by mass, 0.4% to 3.0% by mass, 0.4% to 2.5% by mass, 0.4% to 2.0% by mass, 0.5% to 15% by mass, 0.5% to 12% by mass, 0.5% to 9.0% by mass, 0.5% to 8.0% by mass, 0.5% to 7.0% by mass, 0.5% to 6.0% by mass 0.5% to 5.0% by mass, 0.5% to 4.0% by mass, 0.5% to 3.5% by mass, 0.5% to 3.0% by mass, 0.5% to 2.5% by mass, 0.5% to 2.0% by mass, 0.6% to 15% by mass, 0.6% to 12% by mass, 0.6% to 9.0% by mass, 0.6% to 8.0% by mass, 0.6% to 7.0% by mass, 0.6% to 6.0% by mass, 0.6% to 5.0% by mass, 0.6% to 4.0% by mass, 0.6% to 3.5% by mass, 0.6% to 3.0% by mass, 0.6% to 2.5% by mass, 0.6% to 2.0% by mass 0.8% to 15% by mass, 0.8% to 12% by mass, 0.8% to 9.0% by mass, 0.8% to 8.0% by mass, 0.8% to 7.0% by mass, 0.8% to 6.0% by mass, 0.8% to 5.0% by mass, 0.8% to 4.0% by mass, 0.8% to 3.5% by mass, 0.8% to 3.0% by mass, 0.8% to 2.5% by mass, 0.8% to 2.0% by mass, 1.0% to 15% by mass, 1.0% to 12% by mass, 1.0% to 9.0% by mass, 1.0% to 8.0% by mass, 1.0% to 7.0% by mass, 1.0% to 6.0% by mass, 1.0% to 5.0% by mass, 1.0% to 4.0% by mass, 1.0% to 3.5% by mass, 1.0% to 3.0% by mass, 1.0% to 2.5% by mass, 1.0% to 2.0% by mass, 1.2% to 15% by mass, 1.2% to 12% by mass, 1.2% to 9.0% by mass, 1.2% to 8.0% by mass, 1.2% to 7.0% by mass %, 1.2% to 6.0% by mass, 1.2% to 5.0% by mass, 1.2% to 4.0% by mass, 1.2% to 3.5% by mass, 1.2% to 3.0% by mass, 1.2% to 2.5% by mass, 1.2% to 2.0% by mass, 1.4% to 15% by mass, 1.4% to 12% by mass, 1.4% to 9.0% by mass, 1.4% to 8% by mass 0.0% by mass, 1.4% to 7.0% by mass, 1.4% to 6.0% by mass, 1.4% to 5.0% by mass, 1.4% to 4.0% by mass, 1.4% to 3.5% by mass, 1.4% to 3.0% by mass, 1.4% to 2.5% by mass, 1.4% to 2.0% by mass, 1.5% to 15% by mass, 1.5% to 12% by mass, 1.5% by mass The brush copolymer may be present in the lubricating composition in amounts ranging from 9.0% to 9.0% by mass, 1.5% to 8.0% by mass, 1.5% to 7.0% by mass, 1.5% to 6.0% by mass, 1.5% to 5.0% by mass, 1.5% to 4.0% by mass, 1.5% to 3.5% by mass, 1.5% to 3.0% by mass, 1.5% to 2.5% by mass, or 1.5% to 2.0% by mass. In particular, the brush copolymer may be present in the lubricating composition in amounts ranging from 0.5% to 12% by mass or from 1.0% to 9.0% by mass.

[0055] The base oil for a lubricating oil can be any suitable base oil known in the art. Both natural and synthetic base oils may be suitable. Natural lubricants may include animal fats, vegetable oils (such as castor oil and lard), petroleum, mineral oils, oils derived from coal or shale, and combinations thereof. A particular natural lubricant may include or include mineral oils.

[0056] Suitable mineral oils can include all common mineral oil base oils, including those with a cycloalkane or alkanes chemical structure. Suitable oils can be refined using conventional methods with acids, alkalis, and clay or other reagents (such as aluminum chloride), or they can be extract oils, for example, produced by solvent extraction with solvents such as phenols, sulfur dioxide, furfural, dichlorodiethyl ether, or combinations thereof. They can be hydrotreated or hydrofined, dewaxed by cooling or catalytic dewaxing processes, hydrocracking, or some combination thereof. Suitable mineral oils can be derived from natural crude oil sources or can consist of isomerized wax materials or residues from other refining processes.

[0057] Synthetic lubricants may include hydrocarbon oils and halogenated hydrocarbon oils, such as oligomers, polymers and copolyolefins (e.g., polybutene, polypropylene, propylene-isobutene copolymers, chlorinated polylactenes, poly(1-hexene), poly(1-octene), poly(1-decene) and mixtures thereof); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene and other similar products); polyphenylenes (e.g., biphenyl, terphenyl, alkylated polyphenylenes and other similar products); alkylated diphenyl ethers, alkylated diphenyl sulfides and their derivatives, analogs and homologues; and combinations and / or reaction products thereof.

[0058] In some embodiments, the oil from this class of synthetic oils may contain or be polyalphaolefins (PAOs), including hydrogenated oligomers of alpha-olefins, particularly oligomers of 1-decene, such as those produced by radical, Ziegler catalytic, or cationic processes. These may be, for example, oligomers of branched or linear alpha-olefins having 2 to 16 carbon atoms, and specific, non-limiting examples include polypropylene, polyisobutylene, poly-1-butene, poly-1-hexene, poly-1-octene, poly-1-decene, poly-1-dodecene, and mixtures and / or copolymers thereof.

[0059] Synthetic lubricants may additionally or alternatively include alkylene oxide polymers, interpolymers, copolymers, and their derivatives, wherein any (most) terminal hydroxyl groups have been modified by esterification, etherification, etc. Examples of such synthetic oils may be: polyoxyalkylene polymers produced by polymerization of ethylene oxide or propylene oxide; alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ethers with an average Mn of ~1000 Daltons, polypropylene glycol diphenyl ethers with an average Mn of about 1000 to about 1500 Daltons); and their mono- and polycarboxylic acid esters (e.g., acetate esters, mixed C3-C8 fatty acid esters, C3-C8 esters of tetraethylene glycol). 12 Oxy-acid diesters, or combinations thereof).

[0060] Another suitable class of synthetic lubricants may include esters of dicarboxylic acids (such as phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, octanoic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) and various alcohols (such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicoyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, complex esters formed by reacting 1 mole of sebacate with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid, and combinations thereof. Preferred types of oils from this class of synthetic oils may include C4 to C6 oils. 12 Adipate esters of alcohols.

[0061] Esters that can be used as synthetic lubricants may additionally or alternatively include those composed of C5-C64. 12 Those made from monocarboxylic acids, polyols and / or polyol ethers (e.g., neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.) and combinations thereof.

[0062] This lubricant can be derived from unrefined oil, refined oil, re-refined oil, or mixtures thereof. Unrefined oil is obtained directly from natural or synthetic sources (e.g., coal, shale, or tar sand bitumen) without further purification or treatment. Examples of unrefined oil may include shale oil obtained directly from a dry distillation operation, petroleum obtained directly from distillation, or ester oil obtained directly from an esterification process, each or a combination thereof, which may then be used without further processing. Refined oil is similar to unrefined oil, except that refined oil has typically been treated in one or more purification steps to alter its chemical structure and / or improve one or more properties. Suitable purification techniques may include distillation, hydrotreating, dewaxing, solvent extraction, acid or alkali extraction, filtration, and percolation, all known to those skilled in the art. Re-refined oil can be obtained by treating used and / or refined oil in a process similar to that originally used to obtain refined oil. These re-refined oils may be referred to as regenerated oil or reprocessed oil and are typically further processed using techniques for removing waste additives and oil decomposition products.

[0063] Another class of suitable supplemental or alternative lubricants may include base oils made from oligomers or waxes derived from natural gas feedstocks. These base oils can be referred to in many ways, but they are commonly known as Gas-to-Liquid (GTL) or Fischer-Tropsch basestocks.

[0064] The lubricating oil base stock according to this disclosure may be a blend of one or more oils / base stock described herein, whether similar or different in type, and blends of natural and synthetic lubricating oils (i.e., partially synthetic) are explicitly designed for use in this disclosure.

[0065] Lubricating oils can be classified as listed in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, 14th edition, December 1996, Appendix 1, December 1998, where the oil classifications are as follows:

[0066] a) Group I base oils contain less than 90% saturates and / or more than 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120;

[0067] b) Group II base oils contain 90% or more saturates and 0.03% or less sulfur and have a viscosity index of 80 or more and less than 120;

[0068] c) Group III base oils contain 90% or more saturates and 0.03% or less sulfur and have a viscosity index of 120 or more;

[0069] d) Group IV base oils are polyalphaolefins (PAO); and

[0070] e) Class V base oils include all other base oils not included in Classes I, II, III or IV.

[0071] Specifically, the lubricating oil may contain or be a mineral oil or a mixture of mineral oils, particularly Group I, II, III, and / or IV mineral oils (as classified by API). For example, the lubricating oil base oil (e.g., containing Group I, II, III, and / or IV) may constitute 55% to 98% by mass of the total mass of the lubricant composition (which comprises the lubricating oil base oil component and any lubricant additives, in this case, the brush copolymer), for example, 55% to 95% by mass, 55% to 90% by mass, 55% to 85% by mass, 60% to 98% by mass, 60% to 95% by mass, 60% to 90% by mass, 60% to 85% by mass, 65 ...8% by mass, 60% to 98% by mass, 60% to 98% by mass, 60% to 98% by mass, 60% to 98% by mass, 60% to 85% by mass, 65% to 98% by mass, 60% to 98% Quantity % to 98% by mass, 65% to 95% by mass, 65% to 90% by mass, 65% to 85% by mass, 70% to 98% by mass, 70% to 95% by mass, 70% to 90% by mass, 70% to 85% by mass, 75% to 98% by mass, 75% to 95% by mass, 75% to 90% by mass, 75% to 85% by mass, 80% to 98% by mass, 80% to 95% by mass, 80% to 90% by mass, or 80% to 85% by mass.

[0072] Lubricant additives may include one or more additive components and may be present in a (concentrated) lubricant additive package. Although a (concentrated) additive package typically includes a small amount of lubricating oil base oil or the like to make the additive compatible with the rest of the lubricant composition, the term "additive" herein refers only to the lubricant additive in the lubricant composition, while the term "lubricating oil base oil" refers to all base oils derived from the additive package and those that are the main phase lubricant components. Additionally or alternatively, two or more additives may be added together as an additive package, while one or more other components may be added separately to the lubricating oil base oil and / or the blend used to form the lubricant composition.

[0073] Specifically, the lubricant additive may contain one or more of the following, be essentially composed of one or more of the following, or be one or more of the following: antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, detergents, defoamers, extreme pressure additives, pour point depressants, optional dyes and / or dye stabilizers, and seal swelling control agents.

[0074] Anti-wear additives, as the name suggests, are used to reduce wear in lubricated components (such as motorized drivetrain components like crankcases and / or gearboxes). Some anti-wear components also provide antioxidant properties in addition to their anti-wear function.

[0075] It is known in the art that phosphorus-containing compounds can provide wear protection for metal surfaces under high loads. While not bound by theory, it has been suggested that this is a result of the formation of a phosphite “glass” on the lubricated metal surface.

[0076] The phosphorus-containing anti-wear component may contain one or more, particularly two or more, or three or more compounds of structure (I):

[0077]

[0078] The groups R1, R2, and R3 may each independently comprise or contain an alkyl group having 1 to 18 carbon atoms and / or an alkyl group having 1 to 18 carbon atoms in which the alkyl chain is interrupted by a thioether bond, provided that at least some of the groups R1, R2, and R3 may comprise or contain an alkyl group having 1 to 18 carbon atoms in which the alkyl chain is interrupted by a thioether bond. The mixture may contain three or more, four or more, or five or more compounds of structure (I).

[0079] In some embodiments, groups R1, R2, and R3 may each independently comprise or have an alkyl group having 4 to 10 carbon atoms and / or an alkyl group having 4 to 10 carbon atoms in which the alkyl chain is inserted by a thioether bond, provided that at least some groups R1, R2, and R3 may comprise or have an alkyl group having 4 to 10 carbon atoms in which the alkyl chain is inserted by a thioether bond.

[0080] When groups R1, R2, and R3 contain alkyl groups (where the alkyl chain is not inserted by a thioether bond), examples may include, but are not limited to, methyl, ethyl, propyl, and butyl, particularly including butyl.

[0081] When groups R1, R2, and R3 contain an alkyl group in which the alkyl chain is inserted by a thioether bond, examples include groups with the structure -R'-SR”, where R' can be -(CH2). n -, where n can be an integer from 2 to 4, and R” can be -(CH2). m -CH3, where m can be an integer from 1 to 17, such as from 3 to 9.

[0082] Specifically, for compounds of structure (I), at least 10% by mass (e.g., at least 20%, at least 30%, or at least 40%) of all compounds of structure (I) comprise those in which at least one of R1, R2, and R3 comprises or in which the alkyl chain is inserted by a thioether bond, particularly having the structure -R'-SR", where R' may be -(CH2). n -, where n can be an integer from 2 to 4, and R” can be -(CH2). m -CH3, where m can be an integer from 1 to 17, such as from 3 to 9.

[0083] Another class of phosphorus-containing anti-wear additives may include one or more dialkyl dithiophosphate zinc compounds. Such compounds are known in the art and are commonly referred to as ZDDPs. They can be prepared according to known techniques, for example, by first forming dialkyl dithiophosphate (DDPA) (usually by reacting one or more alcohols or phenols with P2S5), and then neutralizing the formed DDPA with a zinc compound. For example, dithiophosphate can be prepared by reacting a mixture of primary and secondary alcohols. Alternatively, dithiophosphate can be prepared in which the hydrocarbon groups are entirely secondary hydrocarbon groups or entirely primary hydrocarbon groups. To prepare the zinc salt, any basic or neutral zinc compound can be used, but oxides, hydroxides, and carbonates are commonly used. Commercial additives may often contain excess zinc due to the use of an excess of basic zinc compound in the neutralization reaction.

[0084] Advantageous zinc dihydrodithiophosphate may comprise or be an oil-soluble or oil-dispersible salt of dihydrodithiophosphate, such as an oil-soluble or oil-dispersible salt of dihydrodithiophosphate as shown in the following formula:

[0085]

[0086] R8 and R9 can be the same or different hydrocarbon groups containing 1 to 18 (e.g., 2 to 12 or 2 to 8) carbon atoms. Examples of such hydrocarbon groups may include one or more of alkyl, alkenyl, aryl, aralkyl, alkylaryl, and alicyclic groups. Exemplary hydrocarbon groups may include, but are not limited to, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, benzyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, and combinations thereof. To obtain and / or maintain oil solubility and / or oil dispersibility, the total number of carbon atoms on each dialkyl dithiophosphate ligand (i.e., a single R8 and R9 pair) may typically be at least about 5. In particular, zinc dialkyl dithiophosphate may therefore include or be dialkyl zinc dithiophosphate.

[0087] Non-phosphorus-containing anti-wear components, typically present in mixture with phosphorus-containing anti-wear compounds of structure (I), may contain one or more, particularly two or more, compounds of structure (II):

[0088]

[0089] Groups R4 and R7 may each independently comprise or have an alkyl group with 1 to 12 carbon atoms, and R5 and R6 may each independently comprise or have an alkyl bond with 2 to 12 carbon atoms. Specifically, R4 and R7 may each independently comprise or have -(CH2) m-CH3, where m is an integer from 1 to 17, such as from 3 to 9, and R5 and R6 can each independently contain or be -(CH2). n - where n is an integer from 2 to 4. The mixture may contain three or more compounds of structure (II).

[0090] In particular, the mass ratio of the compound of structure (I) to the compound of structure (II) can be 2:1 to 1:2, 3:2 to 2:3 or 4:3 to 3:4.

[0091] Examples of ashless dispersants may include polyisobutylene succinimide, polyisobutylene succinamide, mixed esters / amides of polyisobutylene-substituted succinic acid, hydroxy esters of polyisobutylene-substituted succinic acid, and Mannich condensation products of hydrocarbon-substituted phenols, formaldehyde and polyamines, as well as their reaction products and mixtures.

[0092] Basic nitrogen-containing ashless dispersants are well-known lubricant additives, and their preparation methods are extensively described in patent literature. Exemplary dispersants may include polyisobutylene succinimide and succinamide, wherein the polyisobutylene-substituent is a long chain with more than 36 carbon atoms, such as more than 40 carbon atoms. These materials are readily produced by reacting a dicarboxylic acid material substituted with polyisobutylene with an amine-functionalized molecule. Examples of suitable amines may include polyamines, such as polyalkylene polyamines, hydroxyl-substituted polyamines, polyoxyethylene polyamines, and combinations thereof. Amine functionality may be provided by polyalkylene polyamines, such as tetraethylenepentamine and pentaethylenehexamine. Mixtures in which the average number of nitrogen atoms per polyamine molecule is greater than 7 are also available. These are commonly referred to as heavy polyamines or H-PAMs and may be traded under names such as HPA. TM and HPA-X TM Purchased from Dow Chemical, for E-100 TM Purchased from Huntsman Chemical, etc. Examples of hydroxylated polyamines may include N-hydroxyalkyl-alkylene polyamines, such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, and / or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Patent No. 4,873,009. Examples of polyoxyethylene polyamines may include polyoxyethylene and polyoxypropylene diamines and triamines having an average Mn of about 200 to about 2500 Daltons. This type of product may be traded under the name Jeffamine. TM Purchased.

[0093] As is known in the art, the reaction of amines with polyisobutylene-substituted dicarboxylic acid materials (suitably alkenyl succinic anhydride or maleic anhydride) can be conveniently achieved, for example, by heating the reactants together in an oil solution. Reaction temperatures of ~100°C to ~250°C and reaction times of ~1 to ~10 hours are typical. The reaction ratio can be significantly varied, but a dicarboxylic acid unit content of approximately 0.1 to approximately 1.0 equivalents per reactive amine-containing reactant is generally used.

[0094] Specifically, ashless dispersants may comprise polyisobutylene succinic anhydride and polyalkylene polyamines, such as tetraethylenepentamine or H-PAM, forming polyisobutylene succinimide. The polyisobutylene group may be derived from polyisobutylene and may exhibit a number average molecular weight (Mn) of approximately 750 to approximately 5000 Daltons, for example, approximately 900 to approximately 2500 Daltons. As is known in the art, the dispersant may be post-treated (e.g., with a borating agent and / or with an inorganic acid of phosphorus). Suitable examples can be found, for example, in U.S. Patent Nos. 3,254,025, 3,502,677, and 4,857,214.

[0095] Detergents, such as calcium-containing detergents, are sufficiently oil-soluble or oil-dispersible to remain dissolved or dispersed in oil so as to be carried by the oil to their intended point of action. Calcium-containing detergents are known in the art and include neutral and overbased salts of calcium with acidic substances such as salicylic acid, sulfonic acid, carboxylic acid, alkylphenol, sulfurized alkylphenol, and mixtures thereof.

[0096] Neutral calcium-containing detergents are those detergents that contain a stoichiometric amount of calcium relative to the amount of the (Lewis) acidic structural moiety present in the detergent. Therefore, in general, neutral detergents typically have a relatively low alkalinity compared to their overly alkaline counterparts.

[0097] The term "overbased" (as in the context of calcium neutralizers, for example) is used to indicate the presence of a calcium component in stoichiometric amounts greater than the corresponding (Lewis) acid component. A common method for preparing overbased salts involves heating a mineral oil solution of acid with a stoichiometric excess of a neutralizing agent (in this case, a calcium neutralizer, such as an oxide, hydroxide, carbonate, bicarbonate, sulfide, or a combination thereof, at a temperature of approximately 50°C) at an appropriate temperature and filtering the resulting product. The use of a "promoter" in the neutralization step to facilitate the incorporation of a large excess of salt / base (in this case, calcium) is also known. Examples of compounds that can be used as promoters include, but are not necessarily limited to, phenols such as phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols, and condensation products of formaldehyde with phenols; alcohols such as methanol, 2-propanol, octanol, and Cellosolve. TM alcohol, Carbitol TM Alcohols, ethylene glycol, stearyl alcohol, and cyclohexanol; amines, such as aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, and dodecylamine; and combinations thereof. A particularly efficient method for preparing basic salts involves mixing an acidic substance with an excess of calcium neutralizer and at least one alcohol promoter, and carbonating the mixture at elevated temperatures such as 60 to 200°C.

[0098] Examples of calcium-containing detergents that can be used in the lubricant compositions of this disclosure may include, but are not necessarily limited to, neutral and / or superalkaline salts of such substances, such as calcium phenolate; calcium sulfide (e.g., wherein each aryl group has one or more aliphatic groups to impart solubility to the hydrocarbon); calcium sulfonate (e.g., wherein each sulfonic acid moiety is attached to an aromatic nucleus, which in turn typically contains one or more aliphatic substituents to impart solubility to the hydrocarbon); calcium salicylate (e.g., wherein the aromatic moiety is typically substituted by one or more aliphatic substituents to impart solubility to the hydrocarbon); calcium salts of hydrolyzed phosphorus sulfide alkenes (e.g., having 10 to 2000 carbon atoms) and / or hydrolyzed phosphorus sulfide alcohols and / or aliphatic substituted phenolic compounds (e.g., having 10 to 2000 carbon atoms); calcium salts of aliphatic carboxylic acids and / or aliphatic substituted alicyclic carboxylic acids; and combinations and / or reaction products thereof; and many other similar calcium salts of oil-soluble organic acids. If necessary, a mixture of neutral and / or superalkaline salts of two or more different acids may be used (e.g., one or more superalkaline calcium phenolate and one or more superalkaline calcium sulfonate).

[0099] Methods for producing oil-soluble neutral and superalkaline calcium detergents are well known to those skilled in the art and are widely reported in patent literature. Calcium-containing detergents may optionally undergo post-treatment, such as borylation. Methods for preparing borylated detergents are well known to those skilled in the art and are widely reported in patent literature.

[0100] Antioxidants, sometimes referred to as oxidation inhibitors, can improve the resistance (or reduce susceptibility) of lubricant compositions to oxidation. They work by binding to and modifying oxidants, such as peroxides and other free radical-forming compounds, to render them harmless (e.g., by breaking them down) or by inertizing oxidation catalysts or facilitators. Oxidative degradation can manifest as sludge in fluids with increased use, varnish-like deposits on metal surfaces, and sometimes as increased viscosity.

[0101] Examples of suitable antioxidants include, but are not limited to, copper-containing antioxidants, sulfur-containing antioxidants, aromatic amine and / or amide-containing antioxidants, hindered phenolic antioxidants, dithiophosphates and their derivatives, as well as combinations thereof and certain reaction products. Some antioxidants may be ashless (i.e., virtually free of non-trace or contaminating metal atoms).

[0102] Corrosion inhibitors are used to mitigate the corrosion of metals and are often referred to as metal deactivators or metal passivators. Some corrosion inhibitors can also be characterized as antioxidants.

[0103] Suitable corrosion inhibitors may include nitrogen- and / or sulfur-containing heterocyclic compounds, such as triazoles (e.g., benzotriazole), substituted thiadiazoles, imidazoles, thiazoles, tetraazoles, hydroxyquinolines, oxazolines, imidazoles, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and any one or more derivatives thereof. A specific corrosion inhibitor is benzotriazole, as shown in the following structure:

[0104]

[0105] Where R 10 C1 to C2 are either nonexistent or can be linear or branched, saturated or unsaturated. 20 The compound may contain a hydrocarbon group or a substituted hydrocarbon group. It may contain a ring structure that is alkyl or aromatic in nature and / or contain heteroatoms such as N, O, or S. Examples of suitable compounds may include benzotriazoles, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, alkylaryl- or aralkyl-substituted benzotriazoles, and combinations thereof. For example, the triazole may comprise benzotriazoles and / or alkylbenzotriazoles, wherein the alkyl group contains 1 to about 20 carbon atoms, or 1 to about 8 carbon atoms. Preferred corrosion inhibitors may comprise benzotriazoles and / or tolyltriazoles.

[0106] Additionally or alternatively, corrosion inhibitors may include substituted thiadiazoles with the following structures:

[0107]

[0108] Where R 11and R 12 Independently, it is a hydrogen or hydrocarbon group, which can be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl, and alkylaryl groups. These substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been described in the art, and any such compound may be included in the transmission fluid used in this disclosure. For example, U.S. Patent Nos. 2,719,125, 2,719,126, and 3,087,937 describe the preparation of various 2,5-bis-(hydrodithio)-1,3,4-thiadiazoles.

[0109] Additionally or alternatively, the corrosion inhibitor may include one or more other DMTD derivatives, such as carboxylic acid esters, wherein R 9 and R 10 It can be attached to the sulfur atom of a sulfide via a carbonyl group. The preparation of these sulfide-containing DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. DMTD derivatives prepared by the condensation of DMTD with an α-haloaliphatic monocarboxylic acid having at least 10 carbon atoms are described, for example, in U.S. Patent No. 2,836,564. This method produces DMTD derivatives wherein R... 11 and R 12 It is HOOC-CH(R) 13 )-(R 13 (It is a hydrocarbon group). DMTD derivatives, which are further prepared by amidation or esterification of these terminal carboxylic acid groups, are also available.

[0110] The preparation of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0111] A specific class of DMTD derivatives may include mixtures of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-alkyldithio-1,3,4-thiadiazole. Such mixtures may be marketed under trade names. 4313 is for sale and available from Afton Chemical.

[0112] Friction modifiers may include derivatives of polyethylene polyamines and / or ethoxylated long-chain amines. Derivatives of polyethylene polyamines may advantageously include succinimides with a specified structure or may be simple amides.

[0113] Suitable succinimides derived from polyethylene polyamines may include those with the following structures:

[0114]

[0115] Where x+y can be 8 to 15 and z can be 0 or an integer from 1 to 5, particularly where x+y can be 11 to 15 (e.g., 13) and z can be 1 to 3. The preparation of such friction modifiers is described, for example, in U.S. Patent No. 5,840,663.

[0116] The above-mentioned succinimide can react with acetic anhydride to form friction modifiers with the following structures (where z = 1) as an example:

[0117]

[0118] The preparation of such friction modifiers can be found, for example, in U.S. Patent Application Publication No. 2009 / 0005277. Post-reactions with other reagents, such as boriding agents, are also known in the art.

[0119] An example of an alternative simple amide may have the following structure:

[0120]

[0121] Where R 14 and R 15 They can be the same or different alkyl groups. For example, R 14 and R 15 It can be a linear or branched C 14 To C 20 Alkyl group, and m can be an integer from 1 to 5. Specifically, R 14 and R 15 They can all be derived from isostearic acid, and m can be 4.

[0122] Suitable ethoxylated amine friction modifiers may comprise the reaction products of primary amines and / or diamines with ethylene oxide. The reaction with ethylene oxide may be suitably carried out using stoichiometry so that substantially all primary and secondary amines can be converted to tertiary amines. Such amines may have exemplary structures:

[0123]

[0124] Where R 16 and R 17 It can be an alkyl group containing about 10 to 20 carbon atoms or an alkyl group containing sulfur or oxygen bonds. An exemplary ethoxylated amine friction modifier may include R... 16 and / or R 17 Materials containing 16 to 20 carbon atoms, such as 16 to 18 carbon atoms. This type of material is commercially available and marketed by Akzo Nobel under the trade name. and For sale. Suitable materials from Akzo Nobel may include, in particular, [other materials]. T / 12 and T / 13.

[0125] Another alternative type of friction modifier includes oil-soluble or oil-dispersible molybdenum-containing compounds, such as oil-soluble or oil-dispersible organomolybdenum compounds. Non-limiting examples of such oil-soluble or oil-dispersible organomolybdenum compounds may include, but are not necessarily limited to, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum dithiophosphonate, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, and mixtures thereof, particularly one or more of dialkyl dithiocarbamate, dialkyl dithiophosphate, alkyl xanthate, and alkyl thioxanthate. Representative alkyl xanthate and alkyl thioxanthate compounds may be formulated using the formula Mo(R) 18 OCS2)4 and Mo(R 18 SCS2)4 indicates that each R 18 It may be an organic group selected independently from alkyl, aryl, aralkyl and alkoxyalkyl, typically having 1 to 30 carbon atoms or 2 to 12 carbon atoms, particularly alkyl groups having 2 to 12 carbon atoms each.

[0126] In some embodiments, the oil-soluble or oil-dispersible organic molybdenum compound may comprise molybdenum dithiocarbamate, such as dialkyl dithiocarbamate, and / or may be substantially free of molybdenum dithiophosphate, particularly dialkyl dithiophosphate. In some other embodiments, any oil-soluble or oil-dispersible molybdenum compound may consist of molybdenum dithiocarbamate, such as dialkyl dithiocarbamate, and / or molybdenum dithiophosphate, such as dialkyl dithiophosphate, as the sole source of molybdenum atoms in the lubricant composition. In any set of embodiments, the oil-soluble or oil-dispersible molybdenum compound may consist substantially of molybdenum dithiocarbamate, such as dialkyl dithiocarbamate, as the sole source of molybdenum atoms in the lubricant composition.

[0127] Molybdenum compounds can be mononuclear, binuclear, trinuclear, or tetranuclear, and particularly include or contain binuclear and / or trinuclear molybdenum compounds.

[0128] Suitable dinuclear or dimeric dialkyl dithiocarbamate molybdenum can be represented, for example, by the following formula:

[0129]

[0130] Where R 21 To R 24 Each of the four hydrocarbon groups (R) can independently represent a straight-chain, branched-chain, or aromatic hydrocarbon group having 1 to 24 carbon atoms, and X1 to X4 can each independently represent an oxygen atom or a sulfur atom. 21 To R 24 They may be the same as or different from each other.

[0131] Suitable trinuclear organomolybdenum compounds may include those having the formula Mo3S kL n Q z Those and their mixtures. In such a trinuclear formula, three molybdenum atoms may be attached to multiple sulfur atoms (S), with k ranging from 4 to 7. Additionally, each L can be an independently chosen organic ligand with a sufficient number of carbon atoms to make the compound oil-soluble or oil-dispersible, with n ranging from 1 to 4. Furthermore, when z is non-zero, Q can be selected from neutral electron-donating compounds such as water, amines, alcohols, phosphine, and / or ethers, with z ranging from 0 to 5 and including non-stoichiometric (non-integer) values.

[0132] In such a trinuclear configuration, all ligands (L... n The combination of ligands typically contains at least 21 total carbon atoms (e.g., at least 25, at least 30, or at least 35). However, importantly, the organic groups of the ligands may advantageously collectively exhibit a sufficient number of carbon atoms to make the compound soluble or dispersible in oil. For example, the number of carbon atoms in each ligand L may typically be from 1 to 100, e.g., from 1 to 30 or from 4 to 20.

[0133] Mo3S k L n Q z Trinuclear molybdenum compounds can advantageously exhibit a cationic nucleus surrounded by anionic ligands, as shown by one or both of the following structures:

[0134]

[0135] Such cation nuclei can each have a net charge of +4 (e.g., due to the +4 oxidation state of each Mo atom). Therefore, to dissolve these nuclei, the total charge in all ligands should correspond, in this case, -4. Four monoanion ligands can provide favorable nucleus neutralization. While not wishing to be bound by any theory, it is believed that two or more trinuclear nuclei can be bonded or interconnected by one or more ligands, and these ligands can be polydentate. This includes cases where polydentate ligands have multiple connections to a single nucleus. Oxygen and / or selenium can substitute for a portion of the sulfur atom in either nucleus.

[0136] Non-limiting examples of ligands for the aforementioned trinuclear core may include, but are not necessarily limited to, dithiophosphates such as dialkyl dithiophosphates, xanthates such as alkyl xanthates and / or alkyl thioxanthates, dithiocarbamates such as dialkyl dithiocarbamates, and combinations thereof, particularly each comprising or being a dialkyl dithiocarbamate. Additionally or alternatively, the trinuclear molybdenum-containing ligand may independently be one or more of the following:

[0137]

[0138] Where X5, X6, X7, and Y are each independently oxygen or sulfur, Z is nitrogen or boron, and R 25 R26 R 27 R 28 R 29 R 30 and R 31 Each is independently a hydrogen or organic (carbon-containing) structural moiety, such as a hydrocarbon group, which may be the same as or different from each other, especially the same. Exemplary organic structural moieties may include alkyl (e.g., where the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl, alkylaryl, substituted alkylaryl, aralkyl, substituted aralkyl, ether, thioether, or combinations thereof or reaction products, especially alkyl.

[0139] Oil-soluble or oil-dispersible trinuclear molybdenum compounds can be obtained by using a molybdenum source, such as (NH4)2Mo3S, in a suitable liquid / solvent. 13 ●Prepared by reacting n(H2O) (where n is from 0 to 2, including non-stoichiometric (non-integer) values) with a suitable ligand source, such as tetraalkylthiuram disulfide. In the presence of a molybdenum source (such as (NH4)2Mo3S), the reaction proceeds. 13 ●n(H₂O)), a ligand source (such as tetraalkylthiuram disulfide, dialkyl dithiocarbamate, or dialkyl dithiophosphate), and a sulfur abstracting agent (such as cyanide ions, sulfite ions, or substituted phosphines) in a suitable solvent can form other oil-soluble or oil-dispersible trinuclear molybdenum compounds. Alternatively, a trinuclear molybdenum-sulfur halide salt, such as [M']₂[Mo₃S₇A₆] (where M' is a counterion and A is a halogen, such as Cl, Br, or I), can be reacted with a ligand source (such as dialkyl dithiocarbamate or dialkyl dithiophosphate) in a suitable liquid / solvent (system) to form an oil-soluble or oil-dispersible trinuclear molybdenum compound. A suitable liquid / solvent (system) can be, for example, aqueous or organic.

[0140] Other molybdenum precursors may include acidic molybdenum compounds. These compounds react with basic nitrogen compounds as determined by ASTM D-664 or D-2896 titration procedures and may typically be hexavalent. Examples may include, but are not limited to, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds or combinations thereof. Therefore, molybdenum can be provided to the compositions of this disclosure by molybdenum / sulfur complexes of basic nitrogen compounds as described, for example, in U.S. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195 and 4,259,194 and / or PCT Publication No. WO 94 / 06897.

[0141] Other additives known in the art may be optionally added to lubricant compositions, such as defoamers, sealing swelling control agents, extreme pressure additives, pour point depressants, other viscosity modifiers, optional dyes, and dye stabilizers. They are typically disclosed, for example, in "Lubricant Additives," CVSmallheer and R. Kennedy Smith, 1967, pp. 1-11.

[0142] Additional Implementation Plan

[0143] Additionally or alternatively, this disclosure may include one or more of the following embodiments.

[0144] Implementation Scheme 1. A brush-like copolymer composition comprising a copolymer backbone and copolymer brush arms, wherein:

[0145] The copolymer brush arm comprises repeating units of at least two different acylated poly(alkyleneamine) monomers of formulas (1) and (2):

[0146]

[0147] Among them, each R 5 Independently hydrogen or linear or branched C1-C 24 Alkyl structure portion; each R 6 —Different from each R 5 Despite having similarities with each R 5 Same or greater carbon number — independently linear or branched C8-C 24 The alkyl moiety; y and z are each 1 or 2; and the sum of m+n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arms; and

[0148] The copolymer backbone comprises monomer repeating units of at least two different acrylate monomers of formulas (3) and (4):

[0149]

[0150] Among them, each R 1 and R 3 Independently, it is a hydrogen, linear or branched C1-C4 alkyl moiety or a mixture thereof; each R 2 Independently covalently linked copolymer brush arms, residual hydrogen, residual trisubstituted silyl groups (wherein each substituent is independently a linear, branched, and / or cyclic C1-C8 alkyl, aryl, alkylaryl, or aralkyl structural moiety), residual linear, cyclic, or branched C1-C7 acyl structural moiety, residual linear or branched C1-C4 hydroxyalkyl structural moiety, or residual monovalent counterion; each R 4 Independently linear, branched, and / or cyclic C8-C 30 Alkyl, aryl, alkylaryl, or aralkyl structural moieties; and the sum of a+b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer backbone.

[0151] Implementation Scheme 2. The brush copolymer composition of Implementation Scheme 1, wherein the brush copolymer composition exhibits upper critical dissolution temperature (UCST) behavior at a concentration of ~5 mg / mL in Group III base oils having a kinematic viscosity (KV100) of ~4 cSt at ~100°C.

[0152] Implementation Scheme 3. The brush copolymer composition of Implementation Scheme 2, wherein the UCST behavior is characterized by a major exothermic transition in a differential scanning calorimeter (DSC) at a cooling rate of ~1 °C / min during the second or third cooling portion of repeated heating and cooling cycles, with a peak centered below ~80.0 °C.

[0153] Implementation Scheme 4. The brush copolymer composition of Implementation Scheme 1, wherein the copolymer brush arm exhibits upper critical dissolution temperature (UCST) behavior at a concentration of ~5 mg / mL in Group III base oils having a kinematic viscosity (KV100) of ~4 cSt at ~100°C.

[0154] Implementation Scheme 5. The brush copolymer composition of Implementation Scheme 4, wherein the UCST behavior is characterized by a major exothermic transition in a differential scanning calorimeter (DSC) at a cooling rate of ~1 °C / min during the second or third cooling portion of repeated heating and cooling cycles, with a peak centered below ~80.0 °C.

[0155] Implementation Scheme 6. The brush copolymer composition of Implementation Scheme 1, wherein the polydispersity of the brush copolymer composition, as determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing ~2% triethylamine (TEA) as the eluent at ~40°C against a poly(methyl methacrylate) (PMMA) standard, is less than 1.60.

[0156] Implementation Scheme 7. The brush copolymer composition of Implementation Scheme 1, wherein the polydispersity of the copolymer backbone, the copolymer brush arms, or both, as determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing ~2% triethylamine (TEA) as the eluent at ~40°C and against a poly(methyl methacrylate) (PMMA) standard, is less than 1.60.

[0157] Implementation Scheme 8. The brush copolymer composition of Implementation Scheme 1, wherein the number average molecular weight of the brush copolymer composition, as determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing ~2% TEA as the eluent at ~40°C and against a poly(methyl methacrylate) (PMMA) standard, is from 30,000 g / mol to 100,000 g / mol.

[0158] Implementation Scheme 9. The brush copolymer composition of Implementation Scheme 1, wherein:

[0159] Each R 5 Independently linear or branched C2-C 18 Alkyl or alkenyl structural moiety;

[0160] Each R 6 Independently for linear C8-C 20 Alkyl structure portion;

[0161] Each R 1 and R 3 Independently hydrogen or methyl;

[0162] Each R 2 Independently covalently linked copolymer brush arms, residual hydrogen, or residual linear or branched C1-C4 hydroxyalkyl structural moieties;

[0163] Each R 4 Independently linear or branched C8-C 24 alkyl structural moiety; and

[0164] y and z are both 1.

[0165] Implementation Scheme 10. The brush copolymer composition of Implementation Scheme 1, wherein at least 50 mol% of R 2 The groups are covalently linked copolymer brush arms.

[0166] Implementation Scheme 11. The brush copolymer composition of Implementation Scheme 1, wherein one or more of the following are satisfied:

[0167] The ratio of a:b is 1:14 to 1:2;

[0168] The ratio of m:n is 1:25 to 2:1;

[0169] The sum of a+b is 250 or less; and

[0170] The sum of m+n is 75 or less.

[0171] Implementation Scheme 12. A brush-like copolymer composition comprising a copolymer backbone and copolymer brush arms, wherein:

[0172] The copolymer brush arm exhibits upper critical solution temperature (UCST) behavior at a concentration of ~5 mg / mL in Group III base oils with a kinematic viscosity (KV100) of ~4 cSt at ~100 °C and contains at least two different repeating units of acylated poly(alkyleneamine) monomers of formula (1) and (2):

[0173]

[0174] Among them, each R 5 Independently hydrogen or linear or branched C1-C 24 Alkyl structure portion; each R 6 —Different from each R 5 Despite having similarities with each R 5 Same or greater carbon number — independently linear or branched C8-C 24 The alkyl moiety; and y and z are each 1 or 2; and

[0175] The copolymer backbone comprises monomer repeating units of at least two different acrylate monomers of formulas (3) and (4):

[0176]

[0177] Among them, each R 1 and R 3 Independently, it is a hydrogen, linear or branched C1-C4 alkyl moiety or a mixture thereof; each R 2 Independently covalently linked copolymer brush arms, residual hydrogen, residual trisubstituted silyl groups (wherein each substituent is independently a linear, branched, and / or cyclic C1-C8 alkyl, aryl, alkylaryl, or aralkyl structural moiety), residual linear, cyclic, or branched C1-C7 acyl structural moiety, residual linear or branched C1-C4 hydroxyalkyl structural moiety, or residual monovalent counterion; and each R 4 Independently linear or branched C8-C 30Alkyl, aryl, alkylaryl, or aralkyl structural moiety

[0178] The brush copolymer composition also exhibits upper critical temperature (UCST) behavior at a concentration of ~5 mg / mL in Group III base oils with a kinematic viscosity (KV100) of ~4 cSt at ~100°C.

[0179] Implementation Scheme 13. The brush copolymer composition of Implementation Scheme 12, wherein the UCST behavior of any or both of the copolymer brush arms and the brush copolymer composition is characterized by a major exothermic transition in a differential scanning calorimeter (DSC) at a cooling rate of ~1°C / min during the second or third cooling portion of a repeated heating and cooling cycle, having a peak centered below ~80.0°C.

[0180] Implementation Scheme 14. The brush copolymer composition of Implementation Scheme 12, wherein five or more of the following are satisfied:

[0181] The number-average molecular weight of the brush copolymer composition, determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing ~2% TEA as the eluent at ~40°C and against a poly(methyl methacrylate) (PMMA) standard, is from 30,000 g / mol to 100,000 g / mol.

[0182] Each R 5 Independently linear or branched C2-C 18 Alkyl structure portion; each R 6 Independently for linear C8-C 20 Alkyl structure portion; each R 1 and R 3 Each R is independently hydrogen or methyl; 4 Independently linear or branched C8-C 24 Alkyl structure portion; and y and z are each 1;

[0183] Each R 2 Independently covalently linked copolymer brush arms, residual hydrogen or residual linear or branched C1-C4 hydroxyalkyl structural moieties, and at least 70 mol% of R 2 The groups are covalently linked copolymer brush arms;

[0184] The sum of m+n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arm;

[0185] The ratio of m:n is 1:25 to 2:1;

[0186] The sum of a+b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer backbone;

[0187] The ratio of a:b is 1:14 to 1:2;

[0188] The sum of a+b is 250 or less; and

[0189] The sum of m+n is 75 or less.

[0190] Implementation Scheme 15. A method for manufacturing a brush-like copolymer composition comprising a copolymer backbone and copolymer brush arms, the method comprising:

[0191] Provide a copolymer backbone comprising monomer repeating units of at least two different acrylate monomers of formulas (3) and (4):

[0192]

[0193] Among them, each R 1 and R 3 Independently, it is a hydrogen, linear or branched C1-C4 alkyl moiety or a mixture thereof; each R 2 Independently hydrogen, trisubstituted silyl (wherein each substituent is independently a linear, branched, and / or cyclic C1-C8 alkyl, aryl, alkylaryl, or aralkyl moiety), linear, cyclic, or branched C1-C7 acyl moiety, linear or branched C1-C4 hydroxyalkyl moiety, or monovalent counterion; and each R 4 Independently linear or branched C8-C 30 Alkyl, aryl, alkylaryl, or aralkyl structural moiety;

[0194] Provides copolymer brush arms comprising repeating units of at least two different acylated poly(alkyleneamine) monomers of formulas (1) and (2):

[0195]

[0196] Among them, each R 5 Independently hydrogen or linear or branched C1-C 24 Alkyl structure portion; each R 6 —Different from each R 5 Despite having similarities with each R 5 Same or greater carbon number — independently linear or branched C8-C 24 Alkyl moiety; and y and z are each 1 or 2;

[0197] The copolymer brush arm is manufactured using cationic ring-opening polymerization (CROP) of a heterocyclic monomer containing nitrogen and oxygen atoms, wherein chain-terminated ends are added in a stabilized heterocyclic cation; and

[0198] The copolymer brush arm is grafted onto the copolymer backbone as follows:

[0199] By removing R 2 and / or activate the repeating units of the acrylate monomer of formula (3) in the copolymer backbone by forming carboxylate anions; and

[0200] The stabilized heterocyclic cations in the copolymer brush arm are coupled to the activated repeating unit of formula (3), thereby effectively grafting the copolymer brush arm onto the copolymer backbone and thus forming the brush copolymer composition.

[0201] Implementation Scheme 16. The method of Implementation Scheme 15, wherein the copolymer backbone is manufactured by reversible deactivating free radical polymerization (RDRP).

[0202] Implementation Scheme 17. The method of Implementation Scheme 15, wherein the polydispersity of the brush copolymer composition is less than 1.60, determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing ~2% TEA as the eluent at ~40°C, relative to a poly(methyl methacrylate) (PMMA) standard.

[0203] Implementation Scheme 18. The method of Implementation Scheme 15, wherein the polydispersity of the copolymer backbone, the copolymer brush arm, or both is less than 1.60, as determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing ~2% TEA as the eluent at ~40°C, relative to a poly(methyl methacrylate) (PMMA) standard.

[0204] Implementation Scheme 19. The method of Implementation Scheme 15, wherein the number average molecular weight of the brush copolymer composition is 30,000 g / mol to 100,000 g / mol as determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing 2% TEA as the eluent at ~40°C against a poly(methyl methacrylate) (PMMA) standard.

[0205] Implementation Plan 20. The method of Implementation Plan 15, wherein:

[0206] Each R 5 Independently linear or branched C2-C 18 Alkyl structure portion;

[0207] Each R 6 Independently for linear C8-C 20 Alkyl structure portion;

[0208] Each R 1 and R 3 Independently hydrogen or methyl;

[0209] Each R 2Independently covalently linked copolymer brush arms, residual hydrogen, or residual linear or branched C1-C4 hydroxyalkyl structural moieties;

[0210] Each R 4 Independently linear or branched C8-C 24 alkyl structural moiety; and

[0211] y and z are both 1.

[0212] Implementation Scheme 21. The method of Implementation Scheme 15, wherein the grafting step is controlled to achieve at least 60 mol% R 2 The groups are covalently linked copolymer brush arms.

[0213] Implementation Scheme 22. The method of Implementation Scheme 15, wherein one or more of the following are satisfied:

[0214] The sum of m+n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arm;

[0215] The ratio of m:n is 1:25 to 2:1;

[0216] The sum of a+b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer backbone;

[0217] The ratio of a:b is 1:14 to 1:2;

[0218] The sum of a+b is 250 or less; and

[0219] The sum of m+n is 75 or less.

[0220] Implementation Scheme 23. A lubricant composition comprising:

[0221] At least 70% by weight of one or more lubricating oil base oils;

[0222] Up to 25% by weight of at least one lubricant additive, comprising antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, detergents, defoamers, extreme pressure additives, pour point depressants, sealing swelling control agents, or combinations thereof; and

[0223] 0.5% to 12% by weight of the brush copolymer composition according to embodiment 1.

[0224] Implementation Scheme 24. A lubricant composition comprising:

[0225] At least 70% by weight of one or more lubricating oil base oils;

[0226] Up to 25% by weight of at least one lubricant additive, comprising antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, detergents, defoamers, extreme pressure additives, pour point depressants, sealing swelling control agents, or combinations thereof; and

[0227] 0.5% to 12% by weight of the brush copolymer composition according to embodiment 12.

[0228] Implementation Scheme 25. A lubricant composition comprising:

[0229] At least 70% by weight of one or more lubricating oil base oils;

[0230] Up to 25% by weight of at least one lubricant additive, comprising antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, detergents, defoamers, extreme pressure additives, pour point depressants, sealing swelling control agents, or combinations thereof; and

[0231] 0.5% to 12% by weight of a brush copolymer composition prepared according to the method of embodiment 15, wherein the brush copolymer composition exhibits upper critical dissolution temperature (UCST) behavior at a concentration of ~5 mg / mL in Group III base oils having a kinematic viscosity (KV100) of ~4 cSt at ~100°C.

[0232] Implementation Scheme 26. The lubricant composition of Implementation Scheme 25, wherein the UCST behavior of the brush copolymer composition is characterized by a major exothermic transition in a differential scanning calorimeter (DSC) at a cooling rate of ~1°C / min during the second or third cooling portion of a repeated heating and cooling cycle, with a peak centered below ~85.0°C.

[0233] The invention will now be described only by way of non-limiting embodiments. Example

[0234] The present invention is illustrated in detail below with reference to embodiments, but this is not intended to impose limitations.

[0235] Material

[0236] 2-Ethyl-2-oxazoline (EtOx, 99+%, available from Acros Organics of Geel, Belgium) was dried over calcium hydride and distilled under nitrogen before use. Methyl toluenesulfonate (MeTos, 98%, available from Aldrich of St. Louis, MO, USA) was distilled under reduced pressure and stored under nitrogen. Triethylamine (TEA, ≥99%, available from Sigma-Aldrich) was distilled and stored under nitrogen. The ultra-dry solvents dichloromethane (99.8%) and chlorobenzene (99.8%), available from Acros Organics, were stored on molecular sieves under an inert atmosphere. Titanium n-butoxide (IV) (99%), ethanolamine, and 3-amino-1-propanol (99%), available from Acros Organics, were used as per sample. Initiator V-601, available from Fujifilm Wako Chemicals Corporation, was used as per sample. Monomers methacrylic acid (MAA, 99%, available from Aldrich) and 2-ethylhexyl methacrylate (EHMA, 99%, available from Acros Organics) and transfer agent 2-cyano-2-propyl dithiobenzoate (CPBD, >97%, available from Aldrich) are used as per sample. Sodium methoxide (NaOMe, 95%) and stearic acid (95%), available from Sigma-Aldrich, are used as per sample. Dimethylformamide (DMF, ≥99%) is available from Fisher Chemical of Pittsburgh, PA, USA.

[0237] Other acrylate monomers and macromonomers may be wholly or partially commercially available or synthetic. For example, 2-heptadecyl-2-oxazoline (stearyl oxazoline or SteOx) may be commercially available or manufactured according to the formulation below.

[0238] Monomer Synthesis - Example 1

[0239] In a 500 mL round-bottom flask equipped with a magnetic stir bar, stearic acid (~1.00 eq) was dissolved in MeOH (~30 eq). Sulfuric acid (~0.007 eq) was then added, and the reaction mixture was stirred overnight (~8–18 h) under reflux at ~85 °C. The temperature was then lowered, maintained under reflux until room temperature (~20–25 °C). NaHCO3 was slowly added until no gas release was observed. The solvent was removed under vacuum, and the resulting methyl stearate was used in its ready state. Subsequently, ethanolamine (~4 eq) and sodium methoxide (~3 mol%) were added to the round-bottom flask, which was then placed in an oil bath and heated to ~120 °C overnight. After amination, the reaction mixture was cooled to ~90 °C and distilled under reduced pressure at ~90–160 °C. When ~160 °C was reached, the solution was held at this temperature for ~15 minutes, and then titanium(IV) n-butoxide (~0.14 eq) was added. The reaction mixture was then stirred overnight under reduced pressure at ~160 °C. The obtained 2-oxazoline was obtained by distillation of a crude mixture under reduced pressure at a temperature above ~250°C. A pale yellow solid was given in ~50-65% yield. Exemplary data: 1 ¹H NMR (~300MHz, CDCl₃), δ (ppm): ~0.74-0.85 (m, 3H, CH₂CH₃), ~1.11-1.31 (m, 28H, CH₂alkyl chain), ~1.48-1.60 (m, 2H, CCH₂CH₂), ~2.19 (t, 2H, CCH₂CH₂), ~3.75 (t, 2H, CH₂CH₂O), ~4.14 (t, 2H, NCH₂CH₂).

[0240] Characterization

[0241] Proton nuclear magnetic resonance recordings were performed on Bruker Avance III HD 300MHz and HD 400MHz instruments. 1 ¹H NMR spectra were used. Deuterated chloroform (CDCl₃) was used as the solvent, and the signal of residual protonated chloroform (CHCl₃) at ~7.26 ppm was used as a reference for the chemical shift δ. Data analysis was performed using TopSpin 3.2 software.

[0242] Based on the solubility of the sample, two different eluents were used for gel permeation chromatography (GPC) measurements.

[0243] (i) Tetrahydrofuran (THF) containing ~2% (v / v) TEA (trimethylamine). (Agilent Technologies 1260 Infinity) TM The instrument is equipped with a refractive index (RI) and ~308nm UV detector, PLgel TM ~5μm guard column and PLgelTM ~5 μm mixed D column (~300 x ~7.5 mm). Unless otherwise specified, samples are run at ~40 °C at ~1 mL / min. Poly(methyl methacrylate) standards (Agilent PMMA calibration kits, MM-10 and ML-10) are used for calibration. Samples are filtered through a PTFE membrane with a ~0.2 μL pore size before injection (~100 μL).

[0244] (ii) Chloroform (CHCl3) containing ~2% (v / v) TEA. For Agilent Infinity II. TM The MDS instrument is equipped with differential refractive index (DRI), viscosity measurement (VS), two-angle light scattering (LS), and multi-wavelength UV detectors. The system is equipped with 2xPLgels. TM Mixed C-pillar (~300 x ~7.5 mm) and PLgel TM ~5μm guard column. Samples were run at ~30℃ at ~1mL / min. Poly(methyl methacrylate) and polystyrene standards (Agilent EasiVials) TM For calibration, ethanol was added as a flow marker. The sample was filtered through a GVHP membrane with a pore size of ~0.22 μm before injection (~100 μL). In both cases, experimental molar mass, number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity (Mw / Mn) were determined using Agilent GPC / SEC software via routine calibration (using OriginPro). TM (2019b Academic software drawing).

[0245] Turbidity analysis for determining the transition temperature of each sample was performed using an Agilent Technologies Cary 100UV-Vis spectrophotometer equipped with an Agilent Technologies Cary temperature controller and an Agilent Technologies 6x6 multicell block peltier. The samples were filled with each polymer in YuBase. TM 4. A ~5 mg / mL solution of diluent / base oil (available from SK of South Korea) Quartz cuvettes (100-QS, optical path ≈ 10 mm, available from Hellma of Jena, Germany) were used for measurements. For each sample, two heating / cooling cycles were performed at a temperature gradient of ~1℃ / min at λ≈600nm, ranging from ~15℃ to ~85℃. All data were analyzed using Cary WinUV. TMSoftware recording, using OriginPro TM 2019b (Academic) software refinement. The reported transition temperature is the temperature measured / calculated at ~50% transmission for the second heating and / or second cooling cycle (the first heating cycle is designed to remove any thermal history that may easily distort the results).

[0246] Thermogravimetric analysis (TGA) was performed on a Mettler-Toledo instrument equipped with an autosampler at an air flow rate of ~50 mL / min and a heating rate of ~1 °C / min from ~25 °C to ~550 °C. Samples (~5-20 mg each) were prepared using aluminum trays. Mettler-Toledo STAR was used. eTM Software analysis of data (using OriginPro) TM (2019b Academic software drawing).

[0247] Differential scanning calorimetry (DSC) analysis was used in the Mettler-Toledo DSC1 equipped with an autosampler. TM The thermal transition was measured from -80°C to ~150°C under a nitrogen atmosphere at a flow rate of ~50 mL / min. A heating / cooling rate of ~60°C / min was used for the first cycle (not used for subsequent calculations), and a heating / cooling rate of ~1°C / min was used for the next two heating-cooling cycles. Samples (~5-20 mg each) were prepared using aluminum disks. The thermoelectric effect was measured using a Mettler-Toledo STAR. eTM Software analysis of data (using OriginPro) TM (Graphics generated using Academic software, 2019b). If applicable, the reported thermal transition temperatures are those corresponding to peak maximums or minimums (e.g., crystallization, depending on exothermic tabulation). As with turbidity measurements, the reported transition temperatures are those for the third (and / or second) heating and / or the third (and / or second) cooling cycle (the first heating cycle is designed to remove any thermal history that may easily distort the results).

[0248] Synthesis of Brush Arm Copolymers - Examples 2-7 and Comparative Example AB

[0249] In the brush arm copolymers of Examples 2-7, all copolymers used the same initiator (methyl toluenesulfonate, or MeTos) and monomers, 2-ethyl-2-oxazoline (EtOx) and / or 2-heptadecyl-2-oxazoline (SteOx), and were synthesized under similar monomer / initiator ratios and other reaction conditions. The only difference in the reaction conditions was the different ratios between the comonomers themselves. In these examples, the required amounts of SteOx and EtOx were transferred to microwave-safe vials equipped with magnetic stir bars, then sealed and immersed in an oil bath at ~130°C. The reaction mixture was bubbled with a nitrogen stream for ~30 minutes, and then a MeTos stock initiator solution (~49 mg / mL in anhydrous chlorobenzene) was added.

[0250]

[0251] Although simplified illustrations are provided in the equations above, all EtOx-SteOx copolymers of Examples 2-7 are not considered block copolymers or “block” copolymers – they are considered essentially random copolymers, or close to so. Experimental findings by R. Hoogenboom et al., “High-Throughput Synthesis and Screening of a Library of Random and Gradient Copoly(2-oxazoline)s,” Journal of Combinatorial Chemistry, 8(2), 145-48, show that shorter and longer alkyl-chain oxazoline monomers have relatively similar reactivity ratios.

[0252] Regarding the above equations, the molar ratio of total monomer to initiator in the reaction mixture is approximately 50:1. Subsequently, the reaction mixtures are subjected to cationic ring-opening (co)polymerization (CROP) for the required time to achieve substantially complete conversion (at least 95%, or preferably at least 99%), depending on the final copolymer composition. Using MeTos as the initiator, the "initiator" end is considered to constitute a methyl group, while the active chain end is considered to constitute an oxazolinetonium-type comonomer (balanced with a counter anion such as a hydroxyl group) or simply a covalently bonded oxazolinetonium countering the counter anion itself (e.g., a hydroxyl group). Exemplary data: 1HNMR (~300MHz, CDCl3), δ (ppm): ~0.69-0.91 (m, 6H, CH2CH2CH3, C(=O)OCH2CH3), ~0.91-1.32 (m, 28H, CH2 alkyl chain), ~1.32-1.63 (m, 2H, NC(=O)CH2CH2), ~2.02-2.40 (m, 4H, NC(=O)CH2CH2, NC(=O)CH2CH3), ~3.14-3.58 (m, 8H, CH2 main chain).

[0253] In Comparative Examples A and B, homopolymers of ~100% EtOx and ~100% SteOx were synthesized under conditions similar to those of the copolymers.

[0254] Table 1.

[0255]

[0256] In Table 1, the ratio of SteOx to EtOx monomers varied, while the total monomer concentration to initiator (MeTos) concentration ratio remained constant at approximately 50:1. For all examples and comparative examples, [the following results were obtained]. 1 A monomer conversion of >99% was determined by ¹H NMR spectroscopy (not shown). The CROP reaction yields a well-defined polymer product characterized by relatively low polydispersity (PDI). Mn was obtained by GPC of the copolymers of Examples 2-7 and the EtOx homopolymer of Comparative Example A using THF (w / 2% TEA) as the eluent and a PMMA standard. ms And polydispersity index (PDI, or measured Mw / Mn). As indicated by the asterisks in Table 1, in the case of the SteOx homopolymer of Comparative Example B, due to its lack of solubility in THF, CHCl3 (also w / 2% v / v TEA) was used as the eluent, with PMMA as the standard. From the data reported in Table 1, it can be observed that for all examples and comparative examples, regardless of the eluent used, the measured / experimental Mn (Mn) was [missing information]. ms The value is lower than the theoretical Mn (Mn) th The difference is expected, especially since the PMMA standard used for GPC calibration is thought to exhibit differential hydrodynamic volume change relative to the (co)polymer between eluents. Nevertheless, the conversion results (obtained) 1 The 1H NMR spectrum and the uniform, narrow polydispersity values ​​indicate good polymerization control of the CROP reaction under the reaction conditions.

[0257] The thermal properties of Examples 2-7 and Comparative Example AB were evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). All polymers from these examples and comparative examples exhibited thermal stability up to ~300 °C. For DSC measurements, a first rapid heating / cooling cycle was used at ~60 °C / min from ~-80 °C to ~150 °C to remove the thermal history of the samples, followed by two further cycles at ~1 °C / min. Traces of the third cooling cycle are shown for, for example, the individual homopolymers and copolymers. It can be observed that Examples 2-7 and Comparative Example B each appear to exhibit a predominantly exothermic peak (considered to indicate crystallization or a certain α-transition) within the measured temperature range, while, as expected, Comparative Example A appears to show no thermal transition within the measured temperature range. Since the exothermic peaks indicate an α-transition, they are presumed to imply crystallization upon cooling (and corresponding dissolution upon heating), suggesting upper critical dissolution temperature (UCST) behavior within the measured temperature range. The lack of thermal (α) transition behavior in Comparative Example A indicates no substantial change in orderliness, which in this case suggests relatively uniform solubility over the measured temperature range (although relatively uniform insolubility can be alternatively inferred from DSC data alone, this is not the case for EtOx homopolymers).

[0258] Compared to other copolymers, Examples 2 and 7 appear to exhibit higher thermal transition temperatures, closer to the SteOx homopolymer (Comparative Example B). This is not theoretically deficient, but can be explained by an increase in the overall orderliness of both systems. On the one hand, Example 7 contains the lowest amount of EtOx to obtain a copolymer primarily composed of SteOx. Therefore, the (random) inserted EtOx units appear insufficient to disrupt the orderliness (crystallinity) of the longer alkyl side chains of the SteOx units, which can readily arrange into an ordered structure, thus resulting in a transition temperature closer to Comparative Example B. On the other hand, Example 2 contains the highest amount of EtOx (relative to the other copolymers in the examples); however, the two monomers are copolymerized in approximately equimolar amounts. Again, not theoretically deficient, but given the similar reactivity of these comonomers, it is presumed that they may nearly alternate in the resulting copolymer, which can produce a more ordered system overall compared to other copolymers. Therefore, the polymer chains can more easily assemble and form an ordered structure, leading to a relatively higher exothermic temperature. Examples 3-4 appear to exhibit similar thermal transition temperatures, lower than the SteOx homopolymer of Comparative Example B. Unbound by theory, the non-uniform distribution of these two comonomers along the polymer may complicate the assembly kinetics between polymer chains, resulting in regions of lower order. This is exacerbated in the case of Example 5, which exhibits the lowest thermal transition temperature among these. However, as seen in the case of Example 6, increasing the amount of SteOx and thus decreasing the EtOx content to shift back to a more ordered system appears to result in an increase in the thermal transition temperature.

[0259] The solubility behavior of Examples 2-7 and Comparative Example B in dilution oil / base oil was evaluated using turbidity measurements. The (co)polymers were each mixed with Yubase. TM 4. Mix (dissolved therein) (~5 mg polymer / ml diluent) and then subject to two heating / cooling cycles from ~15°C to ~85°C, with turbidity measured at a wavelength of ~600 nm. The measured curves for the second heating cycle of each sample are shown, for example. All copolymers of Examples 2-7 and Comparative Example B appear to exhibit UCST-type behavior (at higher temperatures, the samples appear soluble in the diluent oil to obtain a substantially clear solution with a transmittance equal to or close to 100%).

[0260] However, as the temperature decreased, the transmittance decreased, and the polymer mixture (solution) became inhomogeneous. While not bound by theory, this inhomogeneity is believed to be attributed to the formation of aggregates, possibly caused by the crystallization of long alkyl chains from the SteOx repeating units. Nevertheless, it is noteworthy that for all samples, the transmittance did not drop to 0% at the lowest temperature, which is considered to mean that the (co)polymer remains slightly soluble in oil even at lower temperatures (e.g., ~15°C). As in the case of DSC analysis, sample mixtures / solutions with a more generally ordered structure (Examples 2, 6, and 7) appear to exhibit relatively higher transition temperatures because, theoretically, higher temperatures would be required to disrupt the crystallinity of the (co)polymer side chains compared to other less ordered associations. By increasing the degree of disorder in the (co)polymer composition, and thus increasing the level of order in the copolymer, the turbidity transition temperature (approximately the temperature at ~50% transmittance) tends to decrease with increasing SteOx content to approximately 90% SteOx / 10% EtOx. The turbidity profile of the copolymer in Example 5 appears to show composite turbidity (possibly both transition temperatures). Unbound by theory, the initial portion of this effect may be caused by the dynamic discrystallization of the SteOx portion of the polymer chain, resulting in a first relatively abrupt phase transition. However, with further increases in temperature, the polymer chain can undergo further thermal expansion, inducing the dissolution of smaller ordered structures or lower crystalline structures, which causes a second, relatively broad transition. For Examples 2-7 and Comparative Example B, Table 2 below reports the results of the second heating (T... UV turb,heat ) and second cooling (T UV turb,cool The turbidity transition temperature (calculated at ~50% transmittance) measured during the cycle and the thermal transition temperature (T) measured during the third cooling stage in the DSC analysis. DSC th,coolIt can be observed that the data are relatively well consistent, indicating that the α-transition (peak exothermic) temperatures in each (co)polymer are similar to those in Yubase. TM The correlation between the temperatures at which the phase transition (the onset of UCST behavior) occurs in 4.

[0261] Table 2.

[0262]

[0263] Synthesis of Brush Arm Copolymers - Examples 8-16 and Comparative Example C

[0264] In the brush arm copolymers of Examples 8-16 and Comparative Example C, various combinations of SteOx, EtOx, 2-(15-methyl)hexadecyl-2-oxazoline (isostearyl oxazoline or isoSteOx) and 2-heptyl-2-oxazoline (HepOx), as well as isoSteOx alone, were used. The same initiator (MeTos) was used for all (co)polymerizations. In Examples 8-9 and Comparative Example C, the total monomer to initiator molar ratio was ~25:1, while in Examples 10-16 it was ~50:1. In each of these examples, the required amount of monomer was transferred to a microwave-safe vial equipped with a magnetic stir bar, then sealed and immersed in an oil bath at ~130°C. The reaction mixture was bubbled with a nitrogen stream for ~30 minutes, and then the initiator solution (~49 mg / mL MeTos in anhydrous chlorobenzene) was added. The reaction time (~60 minutes) required for each reaction mixture to undergo cationic ring-opening (co)polymerization (CROP) under these conditions, in order to achieve the desired result. 1 The reported monomer conversion levels were obtained by 1H NMR. The results are shown in Table 3 below.

[0265] Table 3.

[0266]

[0267] The solubility behavior of Examples 8-16 and Comparative Example C in dilution oil / base oil was evaluated by turbidity measurement, and the results are shown in Table 4 below. The (co)polymers were each mixed with Yubase. TM 4. The mixture (dissolved therein) (~5 mg polymer / ml diluent) was then subjected to two heating / cooling cycles from ~15°C to ~85°C, with turbidity measured at a wavelength of ~600 nm. As in Examples 2-7 and Comparative Example B above, the turbidity transition temperature was approximately the temperature at ~50% transmittance during the heating and cooling cycles. The reported figures are from the second cycle of each type. Furthermore, three heating and cooling cycles were performed in the DSC, and the peak exothermic temperature from the third cooling cycle was reported.

[0268] Table 4.

[0269]

[0270] 1 Measurement within the range of ~15-95℃

[0271] As the data shows, the (co)polymers of Comparative Example C and Examples 9-11 appear to be soluble in Yubase within the turbidity analysis temperature range. TM 4. Example 8 appears to be insoluble in Yubase within the same temperature range. TM 4. Furthermore, only the copolymers of Examples 12-17 appear to exhibit UCST-type behavior (at higher temperatures, the samples appear soluble in diluent oil to obtain essentially transparent solutions with a transmittance equal to or close to 100%). However, it should be noted that although the copolymer of Example 14 appears to exhibit UCST-type behavior, this copolymer did not completely dissolve in Yubase at the higher temperature end of the test protocol. TM In Table 4 (as demonstrated by measurable transmittance levels below 100%), this introduces potential errors into the measured turbidity transition values ​​(marked with an asterisk in Table 4).

[0272] Synthesis of main-chain copolymers - Examples 17-20

[0273] Examples 17-20 describe the synthesis of copolymers of methacrylic acid and 2-ethylhexyl methacrylate in different ratios using reversible addition-fragmentation chain transfer (RAFT) (co)polymerization (a type of reversible deactivating radical (RDRP) copolymerization). In Example 17, methacrylic acid (~0.66 mL, ~7.8 mmol, MAA) and 2-ethylhexyl methacrylate (~7 mL, ~31.2 mmol, EHMA) were transferred to a round-bottom flask equipped with a magnetic stir bar and dissolved in dimethylformamide (DMF) to achieve a final monomer concentration of ~5 mol / L. A solution of ~22.4 mg V-601 initiator in DMF and a solution of ~86 mg 2-cyano-2-propyl dithiobenzoate transfer agent in DMF were added to the flask. The molar ratio of [MAA]:[EHMA]:[CTA]:[I] in Example 17 was ~20:80:1:0.25. Examples 18-20 use the same molar ratio of transfer agent and initiator, but the molar ratio of [MAA]:[EHMA] is ~30:70, ~40:60 and ~50:50, respectively.

[0274]

[0275] Although simplified illustrations are made in the equations shown above, all MAA-EHMA copolymers of Examples 17-20 are not considered to be block copolymers or "block" in nature - they are considered to be essentially random copolymers, or close to that.

[0276] Subsequently, each reaction mixture was bubbled with a nitrogen stream for ~30 minutes, then the flask was capped with a silicone diaphragm and heated in an oil bath to ~70°C for ~20 hours. The copolymers were obtained as pink powders by precipitation into methanol. V-601 (bis[2-cyano-2-propanoate]-1,2-diazepine) was used as the initiator and 2-cyano-2-propanoate dithiobenzoate. The "initiator / CTA" end was considered to constitute the 2-cyano-2-propanoic structural moiety (in this case, both the initiator residue and the CTA residue were considered identical), while the "active" chain end was considered to be reversibly capped with the benzodithioate portion of CTA. Conversion was measured by... 1 H NMR measurements. Example data: 1 H NMR(~400MHz, CDCl3), δ(ppm):~0.72-1.15(m,12H,COOHCCH3,COOCH2CCH3,CHCH2CH3,CH2CH2CH3),~1.16-1.47(m,8H,CHCH2CH3,CHCH 2CH2,CH2CH2CH2,CH2CH2CH3),~1.47-1.64(m,1H,CH2CHCH2),~1.68-2.26(m,4H,CH2CCOOH,CH2CCOOCH2),~3.53-4.15(m,2H,OCH2CH).

[0277] In the MAA-EHMA copolymers of Examples 17-20, only the copolymer with a molar ratio of EHMA to MAA of 4:1 (Example 17) was found to have ideal solubility in dichloromethane (DCM). Since the subsequent reaction of grafting the brush arm copolymer onto the copolyacrylate backbone will be carried out using DCM as a diluent / solvent, only comonomer systems with a molar ratio of at least ~3:1 (~75 / 25 or higher) of acrylate monomers of formulas (4) and (3) were selected for further use. The MAA-EHMA copolymer of Example 17 was analyzed by GPC, and as with most other examples and comparative examples, Mn was obtained by using THF (w / 2% v / v TEA) as the eluent against a PMMA standard at ~40°C. ms And the polydispersity index (PDI, or the measured Mw / Mn). Based on this, Example 17 yielded Mn of 17500 g / mol. ms And PDI of 1.18. Mn in Example 17 th The calculated value is approximately 17800 g / mol, and through... 1 The conversion rate of Example 17, as determined by H NMR, was >95%.

[0278] Brush copolymer grafting reaction - Examples 21-34 and Comparative Example D

[0279] The brush copolymers according to Examples 21-34 and Comparative Example D were prepared in three steps: (1) CROP of the 2-oxazoline monomer to form brush (co)polymer arms (polyOx); (2) RAFT of the (meth)acrylate monomer to form the copolymer backbone (poly(xMA)); and (3) Grafting-onto reaction of the brush (co)polymer arms with the side functional groups of the (meth)acrylate monomer on the copolymer backbone to form various brush copolymer compositions. Since steps (1) and (2) are carried out separately from each other and are independent of each other, they can be carried out in any order or simultaneously, as long as both are carried out before step (3) (which utilizes the products of steps (1) and (2)).

[0280] Step 1 – CROP of the 2-oxazoline monomer was carried out in solution. The required amount of 2-oxazoline monomer was transferred to a microwave-safe flask equipped with a magnetic stir bar, then sealed and immersed in an oil bath at ~100°C. The mixture was bubbled with a nitrogen stream for ~30 minutes, followed by the addition of anhydrous dichloromethane (DCM). The final monomer concentration in the DCM was ~4 mol / L. Subsequently, a MeTos stock solution was added, and the reaction mixture was maintained at ~100°C for ~35 minutes to ~4 hours. 1 Conversion rate was determined by ¹H NMR. The molar ratio of 2-oxazoline monomer to initiator was ~25:1 to ~100:1.

[0281] Step 2 - The RAFT polymerization of methacrylic acid (MAA) and 2-ethylhexyl methacrylate (EHMA) was carried out in a ~5M solution in DMF at ~70°C using 2-cyano-2-propyl dithiobenzoate (CPBD) as a chain transfer agent and V-601 as an initiator. As detailed in Examples 17-20, the effect on the hydrophobicity of the final copolymer was evaluated by varying the ratio between the two monomers. For the solubility of the polymer in the Grafting-onto reaction solvent (dichloromethane), a molar ratio of [MAA] to [EHMA] of 20:80 was selected (the same as in Example 17). The total [monomer]:[CPDB]:[V-601] ratio was 100:1:0.25 (also the same as in Example 17). 1 The monomer conversion rate was determined by 1H NMR.

[0282] Step 3 - A solution of poly(xMA) from Step 2 in anhydrous DCM containing triethylamine (TEA) is added via syringe to a capped microwave-safe vial containing oligo-oxazoline (co)polymer chains that are considered "active" and therefore contain oxazoline ononium chains (or their non-equilibrium isomers, or even their reversibly capped forms). In all but one case, based on the concentration of the carboxylic acid side groups of the repeating units of the MAA monomer, the molar amount of poly(xMA) is calculated to be approximately 1.4 times (~20 / 14 molar ratio, or ~40% excess) of the 2-oxazoline (co)polymer (active) chain ends. In one case (Example 32), based on the concentration of the carboxylic acid side groups of the repeating units of the MAA monomer, the molar amount of poly(xMA) is calculated to be approximately 2.8 times (~20 / 7 molar ratio, or ~180% excess) of the 2-oxazoline (co)polymer (active) chain ends. TEA is included in a consistent amount sufficient to facilitate the Grafting-onto reaction (e.g., ~3 molar excess), for example by aiding in the deprotonation of the carboxylic acid hydrogen to facilitate reaction with the 2-oxazoline (co)polymer chain ends (e.g., oxazoline onions at the 2-oxazoline (co)polymer chain ends). The target concentration of the mixture in step 3 is ~2 mol / L. This mixture is heated to a temperature of ~70°C to ~120°C for ~1 hour. The resulting graft copolymer is analyzed by GPC without further purification, and in addition to molecular weight and PDI, the deconvolution (if desired) and comparison of the integrated peak areas of the unreacted brush arms and brush copolymers are used to aid in calculating the grafting efficiency, also known as brush yield (using OriginPro 2019b Academic software).

[0283]

[0284] Although a simplified diagram of step 3 is shown in the equation above, all repeating units of the main chain and brush arms of this brush copolymer are not considered block copolymers or "block" in nature—they are considered essentially random copolymers, or close to so. Furthermore, the simplified diagram of the ring-opening ethyl oxazoline monomer closest to its connection point with the main chain is arbitrary—it should be understood that any repeating unit can actually be connected at any graft point on the copolymer main chain. For convenience only, the asterisk is used as a placeholder for the initiator and the end of the chain.

[0285] Table 5.

[0286]

[0287]

[0288] Details of step 1 relating to Examples 21-32 are shown in Table 5 above, all of which involve EtOx and SteOx comonomers. Examples 21-24 investigated the effect of CROP reaction time on monomer conversion and molecular weight distribution. Example 22 was considered the most balanced reaction for comparison; therefore, the remaining EtOx-SteOx copolymers were targeted with a CROP reaction time of ~1 hour and a conversion of ~85-90% (the only exception being Example 31, where a higher target degree of copolymerization required an increased CROP reaction time to achieve the target conversion level). Examples 22, 28, and 29 investigated variations in the EtOx-SteOx comonomer ratio at approximately a constant degree of polymerization, which produced the expected changes in the measured brush arm number-average molecular weight, but with little change in the measured brush arm PDI. Examples 22, 30, and 31 investigated variations in the EtOx-SteOx degree of polymerization, which also produced some changes in the measured brush arm number-average molecular weight and only minor changes in the measured brush arm PDI. Although a CROP reaction time of ~1 hour was sufficient to achieve degrees of polymerization of 25 and 50 in Examples 22 and 30, it should be noted that a degree of polymerization of 100 (Example 31) required ~4 times the time to achieve a similar monomer conversion and resulted in a greater deviation of the measured number-average molecular weight from the theoretical value compared to the lower degree of polymerization.

[0289] For step 2 of each of Examples 21-32, the main-chain copolymer synthesized in Example 17 was used. Therefore, the poly(xMA) used in Examples 21-32 were of the same kind, and in all but one examples, the molar amount relative to the oxazoline brush arm copolymer chain ends was also the same (as mentioned above, Example 32 calculated the relative molar amount differently to leave more unreacted methacrylic acid side groups and thus generate fewer oxazoline brush arm grafting points).

[0290] Table 6.

[0291]

[0292]

[0293] Details regarding step 3 of Examples 21-32 are shown in Table 6 above. The grafted brush copolymers exhibit a narrow molecular weight distribution that is substantially consistent with or only slightly higher than that of the brush arm copolymers themselves, strongly suggesting that the Grafting-onto step is a relatively rapid reaction: when poly(xMA) is added to the reaction mixture containing the oxazoline copolymer, the deprotonated carboxylic acid groups of the MAA repeating units on the copolymer backbone appear to react immediately with the (active) oxazoline brush arm chain ends to produce well-defined brush copolymers. As shown in the analysis of Step 1, Examples 21-24 varied the CROP time of the polyOx brush arm reaction, but it appears that Example 22, which included the target conversion, also unexpectedly showed an improved brush yield compared to samples with lower and higher monomer conversions. Therefore, it is probably no coincidence that the grafted brush copolymer of Example 22 also showed the closest agreement between the measured number-average molecular weight and the theoretical value in these four experiments. This only reinforces the selection of the conditions of Example 22 as an example and comparison for further research. Nevertheless, the relatively high brush yields at various monomer conversions in these samples indicate that the Grafting-onto reaction proceeds efficiently even below optimal reaction conditions. Examples 22 and 25-27 investigated variations in grafting reaction temperature, which appears to indicate a relatively linear correlation between grafting temperature and brush yield, with a relatively small effect on molecular weight distribution. It should be noted that slightly more side reactions were observed at lower temperatures (~70 / 80°C) and higher temperatures (~120°C) than at intermediate temperatures (~100°C), which may reduce the solubility of the resulting graft copolymers in hydrocarbon lubricating oils. As shown in the analysis in step 1, Examples 22, 28, and 29 investigated variations in the EtOx-SteOx comonomer ratio at a substantially constant degree of polymerization, which, in addition to the effects shown in the analysis in step 1, also appear to indicate a non-linear relationship between decreased brush yield and increased SteOx content. As shown in the analysis in Step 1, Examples 22, 30, and 31 investigated the variation in the degree of polymerization of EtOx-SteOx at a substantially constant comonomer ratio, which, in addition to the effects shown in the analysis in Step 1, also appeared to indicate a relatively linear decrease in brush yield with increasing degree of polymerization. This indication is perhaps not surprising given the effect of increasing SteOx content on brush yield in Examples 22, 28, and 29. Examples 22 and 32 investigated the effect of reducing the proportion of graft chains / graft anchors (the carboxylic acid ester side-attached structural portions of the repeating methacrylic acid units), which appeared to exhibit slightly lower brush yields and slightly lower measured number-average molecular weights relative to theoretical values. Unsurprisingly, the reactivity / functionality of the carboxylic acid portion of the MAA copolymer decreased. However, the relatively low polydispersity of the brush copolymer (similar to the polydispersity of the brush arms themselves) enhances the resilience of the Grafting-onto reactive chemistry even under suboptimal reaction conditions.

[0294] Table 7.

[0295]

[0296] Except GPC and 1 In addition to 1H NMR analysis, the brush copolymers of Examples 21-32 were analyzed by DSC and turbidity measurement to elucidate the thermal and solution-based transitions. As described above, for DSC measurements, a first rapid heating / cooling cycle was used from ~-80°C to ~150°C at ~60°C / min to remove the thermal history of the samples, followed by two further cycles at ~1°C / min. Since exothermic peaks appear in the DSC output to indicate the α-transition, they were presumed to imply crystallization upon cooling (and corresponding dissolution upon heating), indicating upper critical temperature of dissolution (UCST) behavior over the measured temperature range. The solubility behavior of Examples 21-32 in dilution oils / base oils was evaluated by turbidity measurement. The brush copolymers were each compared with Yubase. TM 4. The mixture (dissolved therein) (~5 mg polymer / mL diluent) was then subjected to two heating / cooling cycles from ~15°C to ~85°C, with turbidity measured at a wavelength of ~600 nm. As mentioned above, the turbidity transition temperature is approximately the temperature at ~50% transmittance during the heating and cooling cycles. The reported figures are from the second cycle for each type. Turbidity and DSC data relating to the measured transition temperatures (where available) are presented in Table 7 above.

[0297] Table 8.

[0298]

[0299] Details of step 1 in Examples 33-34 and Comparative Example D are shown in Table 8 above, along with the CROP description herein. The CROP reactions used for these were all carried out at ~100°C for ~1 hour to achieve the reported conversions. All measured molecular weights are reasonably consistent with theoretical molecular weights, and all polydispersities are relatively narrow / low.

[0300] For step 2 of Examples 33-34 and Comparative Example D, the main-chain copolymer synthesized in Example 17 was used. Therefore, the poly(xMA) used in Examples 33-34 and Comparative Example D were of the same type and had the same molar amount relative to the oxazoline brush arm copolymer chain ends.

[0301] Table 9.

[0302]

[0303]

[0304] Details regarding step 3 of Examples 33-34 and Comparative Example D are shown in Table 9 above. The grafted brush copolymers exhibit a narrow molecular weight distribution largely consistent with the brush arm copolymers themselves. The relatively low brush yields of these samples, at least relative to brush copolymers involving EtOx:SteOx copolymer brush arms, indicate solubility issues in the solvent of step 3, which also implies difficulty in establishing thermal and turbidity transitions. Indeed, DSC experiments confirmed that the brush copolymers of Examples 34 and Comparative Example D were soluble at all temperatures within the analytical range, while the brush copolymer of Example 33 was relatively insoluble at all temperatures within the analytical range. Therefore, none of these samples exhibited upper critical temperature of dissolution (UCST) behavior within the measured temperature range.

[0305] All disclosures of patents, articles, and other materials described herein are incorporated herein by reference in their entirety. Descriptions of compositions comprising, consisting of, or substantially consisting of the various specified components as set forth herein and in the appended claims should be construed as also encompassing compositions made by incorporating said various specified components. The principles, preferred embodiments, and modes of operation of the invention have been described in the foregoing description. However, the invention submitted by the applicant should not be construed as limited to the specific embodiments disclosed, as the disclosed embodiments are considered exemplary rather than restrictive. Modifications can be made by those skilled in the art without departing from the spirit of the invention.

Claims

1. A brush copolymer composition comprising a copolymer backbone and copolymer brush arms, wherein: The copolymer brush arm comprises at least two different monomeric repeat units of acylated poly(alkylene amines) of formula (1) and (2): wherein each R 5 independently is hydrogen or a linear or branched C1-C 24 alkyl moiety; each R 6 is different from each R 5 , although having the same or greater carbon number than each R 5 independently is a linear or branched C8-C 24 alkyl moiety; y and z are each 1 or 2; and the sum of m+n is 90 to 100 mole percent of the average degree of polymerization of the copolymer brush arm; and the copolymer backbone comprises monomer repeat units of at least two different acrylate monomers of formulas (3) and (4): wherein each R 1 and R 3 independently is hydrogen, a linear or branched C1-C4 alkyl moiety or mixtures thereof; each R 2 independently is a covalently linked copolymer brush arm, a residual hydrogen, a residual trisubstituted silyl group, wherein each substituent independently is a linear, branched and / or cyclic C1-C8 alkyl, aryl, alkylaryl or arylalkyl moiety, a residual linear, cyclic or branched C1-C7 acyl moiety, a residual linear or branched C1-C4 hydroxyalkyl moiety or a residual monovalent counterion; each R 4 independently is a linear, branched and / or cyclic C8-C 30 alkyl, aryl, alkylaryl or arylalkyl moiety; and the sum of a+b is 90 to 100 mole percent of the average degree of polymerization of the copolymer backbone.

2. The brush copolymer composition of claim 1, wherein: The polydispersity of one, two, or all of the copolymer backbone, the copolymer brush arm, and the brush copolymer composition is less than 1.60 as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing 2% (v / v) triethylamine TEA as eluent at 40 °C against a poly(methyl methacrylate) (PMMA) standard; and / or the number average molecular weight of the brush copolymer composition is from 30,000 g / mol to 100,000 g / mol as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing 2% (v / v) TEA as eluent at 40 °C against a poly(methyl methacrylate) (PMMA) standard.

3. The brush copolymer composition of claim 1, wherein the brush copolymer composition, the copolymer brush arm, or both exhibit upper critical solution temperature (UCST) behavior in a Group III base stock having a kinematic viscosity at 100 °C (KVioo) of 4 cSt at a concentration of 5 mg / mL.

4. The brush copolymer composition of claim 2, wherein the brush copolymer composition, the copolymer brush arm, or both exhibit upper critical solution temperature (UCST) behavior in a Group III base stock having a kinematic viscosity at 100 °C (KVioo) of 4 cSt at a concentration of 5 mg / mL.

5. The brush copolymer composition of any of claims 1-4, wherein: each R 5 independently a linear or branched C2-C 18 alkyl moiety; each R 6 independently a linear C8-C 20 alkyl moiety; each R 1 and R 3 independently hydrogen or methyl; each R 2 independently a covalently linked copolymer brush arm, a residual hydrogen, or a residual linear or branched C1-C4 hydroxyalkyl moiety; each R 4 independently a linear or branched C8-C 24 alkyl moiety; and y and z are each 1.

6. The brush copolymer composition of any of claims 1-4, wherein at least 50 mol% of R 2 groups are covalently linked copolymer brush arms.

7. The brush copolymer composition of claim 6, wherein at least 60 mole percent of R 2 groups are covalently linked copolymer brush arms.

8. The brush copolymer composition of any one of claims 1-4, 7, wherein the copolymer backbone is made by a reversible deactivation radical polymerization (RDRP) method.

9. The brush copolymer composition of claim 8, wherein the reversible deactivation radical polymerization (RDRP) method is a reversible addition fragmentation chain transfer (RAFT) polymerization method.

10. The brush copolymer composition of any of claims 1-4, 7, 9, wherein one or more of the following is met: the ratio of a:b is 1 : 14 to 1 :2; the ratio of m:n is 1 :25 to 2: 1 ; the sum of a+b is 250 or less; the sum of m+n is 75 or less; and optionally the at least two different monomer repeat units of formula (3) and (4) provide a copolymer backbone having a calculated solubility parameter of at most 9.45 (cal / cm 3 ) 1 / 2 .

11. A brush copolymer composition comprising a copolymer backbone and copolymer brush arms, wherein: The copolymer brush arm exhibits upper critical solution temperature (UCST) behavior in a Group III base stock having a kinematic viscosity at 100 °C (KVioo) of 4 cSt at a concentration of 5 mg / mL and comprises at least two different monomeric repeat units of acylated poly(alkylene amines) of formula (1) and (2): wherein each R 5 independently is hydrogen or a linear or branched C1-C 24 alkyl moiety; each R 6 is different from each R 5 , although having the same or greater carbon number than each R 5 independently is a linear or branched C8-C 24 alkyl moiety; and y and z are each 1 or 2; and the copolymer backbone comprises at least two different monomer repeat units of acrylic ester monomers of formula (3) and (4): wherein each R 1 and R 3 is independently hydrogen, a linear or branched C1-C4 alkyl moiety or mixtures thereof; each R 2 is independently a covalently linked copolymer brush arm, a residual hydrogen, a residual trisubstituted silyl group, wherein the substituents are each independently a linear, branched and / or cyclic C1-C8 alkyl, aryl, alkylaryl or arylalkyl moiety, a residual linear, cyclic or branched C1-C7 acyl moiety, a residual linear or branched C1-C4 hydroxyalkyl moiety or a residual monovalent counterion; and each R 4 is independently a linear or branched C8-C 30 alkyl, aryl, alkylaryl or arylalkyl moiety, wherein the brush copolymer composition also exhibits upper critical solution temperature (UCST) behavior at a concentration of 5 mg / mL in a Group III base stock having a kinematic viscosity at 100°C (KV100) of 4 cSt.

12. The brush copolymer composition of claim 11, wherein: The polydispersity of one, two, or all of the copolymer backbone, the copolymer brush arm, and the brush copolymer composition is less than 1.60 as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing 2% (v / v) triethylamine TEA as eluent at 40 °C against a poly(methyl methacrylate) (PMMA) standard; and / or the number average molecular weight of the brush copolymer composition is from 30,000 g / mol to 100,000 g / mol as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing 2% (v / v) TEA as eluent at 40 °C against a poly(methyl methacrylate) (PMMA) standard.

13. The brush copolymer composition of claim 11, wherein the brush copolymer composition, the copolymer brush arm, or both exhibit upper critical solution temperature (UCST) behavior in a Group III base stock having a kinematic viscosity at 100°C (KVioo) of 4 cSt at a concentration of 5 mg / mL.

14. The brush copolymer composition of claim 12, wherein the brush copolymer composition, the copolymer brush arm, or both exhibit upper critical solution temperature (UCST) behavior in a Group III base stock having a kinematic viscosity at 100°C (KVioo) of 4 cSt at a concentration of 5 mg / mL.

15. The brush copolymer composition of any of claims 11-14, wherein: each R 5 independently a linear or branched C2-C 18 alkyl moiety; each R 6 independently a linear C8-C 20 alkyl moiety; each R 1 and R 3 independently hydrogen or methyl; each R 2 independently a covalently linked copolymer brush arm, a residual hydrogen, or a residual linear or branched C1-C4 hydroxyalkyl moiety; each R 4 independently a linear or branched C8-C 24 alkyl moiety; and y and z are each 1.

16. The brush copolymer composition of any of claims 11-14, wherein at least 50 mol% of R 2 groups are covalently linked copolymer brush arms.

17. The brush copolymer composition of claim 16, wherein at least 60 mole percent of R 2 groups are covalently linked copolymer brush arms.

18. The brush copolymer composition of any one of claims 11-14, 17, wherein the copolymer backbone is made by a reversible deactivation radical polymerization (RDRP) method.

19. The brush copolymer composition of claim 18, wherein the reversible deactivation radical polymerization (RDRP) method is a reversible addition fragmentation chain transfer (RAFT) polymerization method.

20. The brush copolymer composition of any of claims 11-14, 17, 19, wherein one or more of the following is met: the ratio of a:b is 1 : 14 to 1 :2; the ratio of m:n is 1 :25 to 2: 1 ; the sum of a+b is 250 or less; the sum of m+n is 75 or less; and optionally the at least two different monomeric repeat units of formula (3) and (4) provide a copolymer backbone having a calculated solubility parameter of at most 9.45 (cal / cm 3 ) 1 / 2 .

21. The brush copolymer composition of any one of claims 11-14, 17, and 19, wherein one or more of the following conditions are satisfied: the sum of m+n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arms; the m:n ratio is 1:25 to 2:1; the sum of a+b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer backbone; the a:b ratio is 1:14 to 1:2; the sum of a+b is 250 or less; the sum of m+n is 75 or less; and optionally, the monomer repeating units of at least two different formulas (3) and (4) provide a content of 8.60 (cal / cm³). 3 ) 1 / 2 Up to 9.45 (cal / cm) 3 ) 1 / 2 The solubility parameters of the copolymer backbone are calculated.

22. The brush copolymer composition of any of claims 11-14, 17, 19, wherein three or more, five or more, seven or more, or all of the following are satisfied: the number average molecular weight of the brush copolymer composition is from 30,000 g / mol to 100,000 g / mol as measured against poly(methyl methacrylate) (PMMA) standards using gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing 2% (v / v) TEA as eluent at 40 °C; each R 5 is independently a linear or branched C2-C 18 alkyl moiety; each R 6 is independently a linear C8-C 20 alkyl moiety; each R 1 and R 3 are independently hydrogen or methyl; each R 4 is independently a linear or branched C8-C 24 alkyl moiety; and y and z are each 1; each R 2 is independently a covalently attached copolymer brush arm, a residual hydrogen, or a residual linear or branched C1-C4 hydroxyalkyl moiety, and at least 70 mole percent of the R 2 groups are covalently attached copolymer brush arms; the sum of m+n is from 90 mole percent to 100 mole percent of the average degree of polymerization of the copolymer brush arms; the ratio of m:n is from 1:25 to 2:1; the sum of a+b is from 90 mole percent to 100 mole percent of the average degree of polymerization of the copolymer backbone; the ratio of a:b is from 1:14 to 1:2; the sum of a+b is 250 or less; the sum of m+n is 75 or less; and optionally the at least two different monomer repeat units of formula (3) and (4) provide a copolymer backbone having a calculated solubility parameter of from 8.80 (cal / cm 3 ) 1 / 2 to 9.44 (cal / cm 3 ) 1 / 2 .

23. A method of making a brush copolymer composition comprising a copolymer backbone and copolymer brush arms, the method comprising: a copolymer backbone is provided comprising monomer repeat units of at least two different acrylate monomers of formula (3) and (4): wherein each R 1 and R 3 is independently hydrogen, a linear or branched C1-C4 alkyl moiety or mixtures thereof; each R 2 is independently hydrogen, a trisubstituted silyl group wherein each substituent is independently a linear, branched and / or cyclic C1-C8 alkyl, aryl, alkylaryl or arylalkyl moiety, a linear, cyclic or branched C1-C7 acyl moiety, a linear or branched C1-C4 hydroxyalkyl moiety or a monovalent counterion; and each R 4 is independently a linear or branched C8-C 30 alkyl, aryl, alkylaryl or arylalkyl moiety, optionally wherein the at least two different monomer repeat units of formula (3) and (4) provide a copolymer backbone having a calculated solubility parameter of at most 9.46 (cal / cm 3 ) 1 / 2 A copolymer brush arm comprising at least two different monomer repeat units of formula (1) and (2) of acylated poly(alkylene amines): wherein each R 5 independently is hydrogen or a linear or branched C1-C 24 alkyl moiety; each R 6 is different from each R 5 , although having the same or greater carbon number than each R 5 independently is a linear or branched C8-C 24 alkyl moiety; and y and z are each 1 or 2; wherein the copolymer brush arm is made by cationic ring-opening polymerization (CROP) process using a heterocyclic monomer containing nitrogen and oxygen atoms, with addition of a chain end termination in a stabilized heterocyclic cation; and the copolymer brush arm is grafted onto the copolymer backbone by activating the acrylic ester monomer repeat units of formula (3) in the copolymer backbone by removal of R 2 and / or formation of carboxylate anions; and coupling of the stabilized heterocyclic cation in the copolymer brush arm to the activated repeat units of formula (3), thereby grafting the copolymer brush arm onto the copolymer backbone and thereby forming the brush copolymer composition.

24. The method of claim 23, wherein: one, two, or all of the copolymer backbone, the copolymer brush arm, and the brush copolymer composition have a polydispersity of less than 1.60 as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing 2% (v / v) triethylamine TEA as eluent at 40°C against a poly(methyl methacrylate) (PMMA) standard; and / or the brush copolymer composition has a number average molecular weight of 30,000 g / mol to 100,000 g / mol as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing 2% (v / v) TEA as eluent at 40°C against a poly(methyl methacrylate) (PMMA) standard.

25. The method of claim 23, wherein the brush copolymer composition, the copolymer brush arm, or both exhibit upper critical solution temperature (UCST) behavior in a Group III base stock having a kinematic viscosity at 100°C (KVioo) of 4 cSt at a concentration of 5 mg / mL.

26. The method of claim 24, wherein the brush copolymer composition, the copolymer brush arm, or both exhibit upper critical solution temperature (UCST) behavior in a Group III base stock having a kinematic viscosity at 100°C (KVioo) of 4 cSt at a concentration of 5 mg / mL.

27. The method of any one of claims 23-26, wherein: each R 5 independently a linear or branched C2-C 18 alkyl moiety; each R 6 independently a linear C8-C 20 alkyl moiety; each R 1 and R 3 independently hydrogen or methyl; each R 2 independently a covalently linked copolymer brush arm, a residual hydrogen, or a residual linear or branched C1-C4 hydroxyalkyl moiety; each R 4 independently a linear or branched C2-C 24 alkyl moiety; and y and z are each 1.

28. The method of any one of claims 23-26, wherein at least 50 mole percent of R 2 groups are covalently linked co-polymer brush arms.

29. The method of claim 28, wherein at least 60 mole percent of R 2 groups are covalently linked co-polymer brush arms.

30. The method of any one of claims 23-26, 29, wherein the copolymer backbone is made by a reversible deactivation radical polymerization (RDRP) method.

31. The method of claim 30, wherein the reversible deactivation radical polymerization (RDRP) method is a reversible addition fragmentation chain transfer (RAFT) polymerization method.

32. The method of any of claims 23-26, 29, 31, wherein one or more of the following are met: the sum of m+n is from 90 mole percent to 100 mole percent of the average degree of polymerization of the copolymer brush arm; the ratio of m:n is from 1 :25 to 2: 1; the sum of a+b is from 90 mole percent to 100 mole percent of the average degree of polymerization of the copolymer backbone; the ratio of a:b is from 1 : 14 to 1 :2; the sum of a+b is 250 or less; the sum of m+n is 75 or less; and optionally the at least two different monomer repeat units of formula (3) and (4) provide a copolymer backbone having a calculated solubility parameter of from 8.60 (cal / cm 3 ) 1 / 2 to 9.45 (cal / cm 3 ) 1 / 2 .

33. The method of any of claims 23-26, 29, 31, wherein three or more, five or more, seven or more, or all of the following are satisfied: the number average molecular weight of the brush copolymer composition is from 30,000 g / mol to 100,000 g / mol as measured against poly(methyl methacrylate) (PMMA) standards using gel permeation chromatography (GPC) with tetrahydrofuran (THF) containing 2% (v / v) TEA as eluent at 40 °C; each R 5 is independently a linear or branched C2-C 18 alkyl moiety; each R 6 is independently a linear C8-C 20 alkyl moiety; each R 1 and R 3 is independently hydrogen or methyl; each R 4 is independently a linear or branched C8-C 24 alkyl moiety; and y and z are each 1; each R 2 is independently a covalently attached copolymer brush arm, a residual hydrogen, or a residual linear or branched C1-C4 hydroxyalkyl moiety, and at least 70 mole % of R 2 groups are covalently attached copolymer brush arms; the sum of m+n is from 90 mole % to 100 mole % of the average degree of polymerization of the copolymer brush arms; the ratio of m:n is from 1:25 to 2:1; the sum of a+b is from 90 mole % to 100 mole % of the average degree of polymerization of the copolymer backbone; the ratio of a:b is from 1:14 to 1:2; the sum of a+b is 250 or less; the sum of m+n is 75 or less; and optionally the at least two different monomer repeat units of formula (3) and (4) provide a copolymer backbone having a calculated solubility parameter of from 8.80 (cal / cm 3 ) 1 / 2 to 9.44 (cal / cm 3 ) 1 / 2 .

34. A lubricant composition comprising: at least 70 wt.% of one or more lubricating oil base stocks; up to 25 wt.% of at least one lubricant additive comprising an antioxidant, a corrosion inhibitor, an antiwear additive, a friction modifier, a dispersant, a detergent, an antifoam agent, an extreme pressure additive, a pour point depressant, a seal swell control agent, or a combination thereof; and 0.5 wt.% to 12 wt.% of the brush copolymer composition according to any one of claims 1-22 or the brush copolymer composition made according to any one of claims 23-33.

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