Thermoresponsive brush polymer having copolymer backbone and copolymer arms

Abstract

The present invention relates to brush copolymer compositions comprising a copolymer backbone having monomer repeat units of at least two different acrylate monomers, and copolymer brush arms having at least two different acylated poly(alkyleneamines). The brush arms, brush copolymer, or both may advantageously exhibit upper critical solution temperature (UCST) behavior, for example in a hydrocarbon diluent. Methods for forming such copolymers utilizing reversible addition fragmentation chain transfer (RAFT) and reversible deactivation radical polymerization (CROP) (pseudo) living reaction methods 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 may be useful for adjusting the viscosity of lubricant compositions (e.g., for passenger car, high-load diesel, and / or marine diesel engines) or other functional fluids such as manual / automatic transmission fluids. More specifically, such brush copolymers may have a poly(meth)acrylate copolymer backbone on which acylated poly(alkyleneamine) copolymers, such as polyoxazoline, may be grafted. Lubricant compositions containing such brush copolymers and methods for producing such brush copolymers are also described herein. [Background technology]

[0002] Living cationic ring-opening polymerization (CROP) of 2-oxazolines has been reported by four independent research groups: T. Kagiya et al., "Ring-Opening Polymerization of 2-Substituted 2-Oxazolines," Journal of Polymer Science Part B: Polymer Letters, 1966, No. 4(7), pp. 441-445; W. Seeliger et al., "Recent Syntheses and Reactions of Cyclic Imidic Esters," Angewandte Chemie International Edition in English, 1966, No. 5(10), pp. 875-888; DATomalia et al., "Homopolymerization of 2-alkyl- and 2-aryl-2-oxazolines," Journal of Polymer Science Part A-1: ​​Polymer Chemistry, 1966, No. 4(9), pp. 2253-2265; and TGBassiri et al., "Polymerization of Cyclic Since its initial report in 1966 in "Immino Ethers. I. Oxazolines," Journal of Polymer Science Part B: Polymer Letters, 1967, No. 5(9), pp. 871-879), 2-oxazoline monomers and their corresponding poly(2-alkyl-2-oxazoline) derivatives have attracted considerable interest, particularly in the development of high-performance polymer materials for biomedical applications. Under appropriate conditions, CROP of 2-oxazoline can proceed in a living or semi-living manner, following the typical mechanism of chain growth polymerization. (See B. Verbraeken et al., "The Chemistry of Poly(2-oxazoline)s," European Polymer Journal, 2017, No. 88, pp. 451–469.) The living properties of polymerization allow for the synthesis of not only clearly defined homopolymers, but also clearly defined random copolymers and block copolymers, depending on the reactivity of the 2-oxazoline monomer. See S. Kobayashi et al., "Block Copolymers from Cyclic Imino Ethers": "A New Class of Nonionic Polymer Surfactant", Macromolecules, 1986, No. 19(3), pp. 535-541; T. Saegusa et al., "One-Shot Block Copolymerization", Macromolecular Chemistry Makromolecular Symposia, 1990, No. 31(1), pp. 1-10.

[0003] Furthermore, by changing the substituent at position 2 of the 2-oxazoline ring, the structure and physical properties of poly(2-alkyl-2-oxazoline) compounds can be precisely controlled and adjusted according to the desired application. In addition to linear copolymers, various structures obtained by copolymerization with other monomers have been reported in the literature (for example, E. Rossegger et al., "Design Strategies for Functionalized Poly(2-oxazoline)s and Derived Materials," Polymers, 2013, No. 5(3), pp. 956-1011; H. Schlaad et al., "Poly(2-Oxazoline)s as Smart Bioinspired Polymers," Macromolecular Rapid Communications, 2010, No. 31(6), pp. 511-525; D. Pizzi et al., "Poly(2-Oxazoline)Macromonomers as Building Blocks for Functional and Biocompatible Polymer Architectures," European Polymer Journal, 2019, No. 121, pp. 109-258). Among these, (co)polymers of brush polymers and graft polymers are attracting considerable attention because they allow for the combination of properties of different polymer units within the same molecule, thus expanding the possibilities for various potential applications. Three synthesis methods may be used for the synthesis of graft copolymers: (i) grafting-through method, (ii) grafting-from method, and (iii) grafting-onto method. However, poly(2-alkyl-2-oxazoline)-based graft structures are rare. These graft structures are mainly synthesized by graft-through methods, in which living oxazolinium species are end-capped with (meth)acrylates and then (co)polymerized with other monomers.

[0004] On the one hand, the use of living polymerization technology can offer many advantages (namely, good control over the molecular weight, dispersibility, and polymer structure of the resulting polymer, clearly defined end groups, and easy synthesis of block copolymers). On the other hand, conventional free radical polymerization allows for the (co)polymerization of a wide variety of monomers due to its easy reaction conditions and high resistance to many functional groups. However, free radical polymerization usually results in termination reactions, making it difficult to obtain clearly defined (co)polymers (A. Rudin et al., "Free-Radical Polymerization," The Elements of Polymer Science & Engineering, 3rd edition; Academic Press: 2013; pp. 341-389). Therefore, the development of a method that combines the advantages of living polymerization with the versatility of free radical polymerization is attracting attention in the field of polymer chemistry. 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 giving living properties to radical polymerization. Because RAFT polymerization tends to have relatively simple reaction conditions and relatively high functional group tolerance, it is possible to polymerize a wide range of monomers (broader than NMP and ATRP) over a wide temperature range and with a rich selection of solvents. Thus, combining the CROP and RAFT polymerization techniques described herein has the potential to provide a powerful tool for obtaining clearly defined polymers. These polymers have precise structures and are based on poly(2-alkyl-2-oxazoline) and RAFT monomers.

[0005] The ability to combine hydrophilic and hydrophobic monomers to form clearly defined polymers with specific polymer structures opens up a wide range of application possibilities. In particular, due to their amphiphilic nature, these polymers can self-aggregate in solution to form nanoscale objects. This self-aggregation behavior can also be induced by external stimuli, making them valuable and versatile candidates for a wide range of applications. Temperature-responsive polymers are attracting particular attention due to their potential applications in biomedical fields, water recovery strategies, and construction. However, the temperature-responsive behavior of linear (co)polymers and (co)polymers with more complex structures has been studied particularly in pure water and alcohol / water mixtures. In fact, there are limited studies reporting temperature-responsive polymers in non-aqueous media.

[0006] Linear poly(octadecyl vinyl ethers) have been observed to undergo an upper critical solution temperature (UCST) phase transition at around 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 Living Cationic Polymerization," Journal of Polymer Science Part A: Polymer Chemistry, 2005, No. 43(6), pp. 1155-1165). [Overview of the Initiative]

[0007] Polystyrene-polyisoprene block copolymers can form cylindrical micelles or vesicles in heptane at room temperature, depending on the length of the isoprene block, and may also reversibly change into spherical or cylindrical micelles when heated to approximately 40°C. Poly(styrene-dimethylsiloxane) diblock copolymers can self-aggregate into vesicles in various dialkyl phthalates at room temperature. As the temperature rises and solvent selectivity decreases, a reversible morphological change from vesicles to cylindrical and then to spherical micelles may be observed. The poly(lauryl methacrylate-block-styrene-block-lauryl methacrylate) gradient copolymer can form spherical colloidal micelles in commercially available aliphatic oils. These spherical colloidal micelles swell when the temperature is increased because the domains, which are a mixture of the two types of blocks, are solubilized in stages. It has been found that the worm-like phase obtained by polymerization-induced self-aggregation (PISA) of a diblock copolymer consisting of benzyl methacrylate and lauryl methacrylate can form a soft, self-supporting gel in n-dodecane at approximately 20°C. When heated to temperatures above approximately 50°C, this gel can degelle by transitioning from a worm-like to a spherical shape. This process is irreversible in dilute solutions (approximately 0.10% mass / mass), but may become reversible as the polymer concentration increases (approximately 20% mass / mass).

[0008] A block copolymer of stearyl methacrylate and 3-phenylpropyl methacrylate can form a pure worm-like phase in n-octane, which becomes a physical gel at room temperature. When heated, the gel transforms into a free-flowing solution, which is thought to be due to a morphological transition from worm-like to spherical nanoparticles caused by a change in the solvation of the 3-phenylpropyl methacrylate block. All-acrylic diblock copolymer nanoparticles composed of lauryl acrylate and benzyl acrylate may exhibit similar behavior in n-dodecane. Recently, the thermally responsive behavior of diblock copolymer vesicles of stearyl methacrylate and benzyl methacrylate, directly prepared in mineral oil by PISA, has been studied. In this case as well, the diblock copolymer can undergo a phase transition from the vesicle phase to the worm-like phase when heated. UCST-type behavior in polyalphaolefins (PAOs) has been observed in homopolymers and random copolymers of alkyl methacrylate monomers with appropriate alkyl pendant lengths. Furthermore, a series of ABA triblock copolymers, including PAO affinity intermediate blocks and temperature-responsive outer blocks, have been synthesized by RAFT polymerization using bifunctional chain transfer agents. At appropriate block compositions and concentrations, the triblock copolymers have been shown to exhibit tunable, thermoreversible sol-gel transitions.

[0009] Graft copolymers consisting of butyl and lauryl methacrylate and a grafted polyolefin skeleton 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, the solubility of the methacrylate side chains increases, which appears to promote deaggregation into single chains. Finally, the solution behavior of linear polydimethylsiloxane-poly(2-(dimethylamino)ethyl methacrylate) diblock copolymers in decamethylcyclopentasiloxane silicone oil has recently been studied: the diblock copolymers appear to undergo a worm-to-spherical transition upon heating due to reversible solvent plasticization of the poly(2-(dimethylamino)ethyl methacrylate) core.

[0010] Furthermore, even in the case of poly(2-alkyl-2-oxazoline)-based materials, their tunable temperature-responsive behavior has only been studied in pure water or water / alcohol mixtures. For example, the temperature-responsive behavior of 2-ethyl-2-oxazoline and 2-isopropyl-2-oxazoline homopolymers has been widely reported. These have been shown to exhibit a lower critical solution temperature (LCST) in aqueous solutions (P. Lin et al., "Solubility and Miscibility of Poly(Ethyl Oxazoline)", Polymer Physics, 1988, No. 26(3), pp. 603-619; U. Hiroshi et al., "A Novel Thermo-Sensitive Polymer. Poly(2-Iso-Propyl-2-Oxazoline)", Chemistry Letters, 1992, No. 21(9), pp. 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, No. 37(7), pp. 2556-2562; JSPark et al., "Versatile Synthesis of End-Functionalized Thermosensitive "Poly(2-Isopropyl-2-Oxazolines)", Macromolecules, 2004, No. 37(18), pp. 6786-6792; M. Meyer et al., "Unexpected Thermal Characteristics of Aqueous Solutions of Poly(2-Isopropyl-2-Oxazoline)", Soft Matter, 2007, No. 3(4), pp. 430-431; S.Huber et al., "Effect of End Group Polarity Upon the Lower Critical Solution Temperature of Poly(2-Isopropyl-2-Oxazoline)," Colloid and Polymer Science, 2008, No. 286 (14-15), pp. 1653-1661; Y. Jung et al., "Linear and Cyclic Poly(2-Isopropyl-2-Oxazoline)s for Fine Control of Thermoresponsiveness," European Polymer Journal, 2017, No. 88, pp. 605-612). The LCST (Low Critical Solution Temperature) can be precisely controlled by copolymerizing 2-oxazoline monomers with different alkyl side chain lengths and, consequently, different hydrophilic / hydrophobic ratios.

[0011] Furthermore, more complex structures are being studied to improve the properties of the final material and enhance control over the temperature range of the phase transition. Among these, comb-type copolymers and graft copolymers based on poly(2-alkyl-2-oxazoline) that can control LCST in aqueous solutions are attracting considerable interest due to their potential applications. However, despite numerous studies on 2-oxazoline polymers exhibiting LCST behavior, there are few reports of polyoxazolines exhibiting an upper critical solution temperature (UCST) phase transition, and those that have been reported only involve phase transitions occurring in alcohol / water mixed solutions.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,” Journal of Polymer Science Part A: Polymer Chemistry, 2009, Issue 47(2), pp. 515-522, Issue 81, pp. 89-91; HML Lambermont-Thijs et al., “Temperature Induced Solubility Transitions of Various Poly(2-Oxazoline)s in Ethanol-Water Solvent R. Hoogenboom et al., “A Schizophrenic Gradient Copolymer”: “Switching and Reversing Poly(2-Oxazoline) See "Micelles Based on UCST and Subtle Solvent Changes," Soft Matter, 2009, No. 5(19), pp. 3590–3592; R. Hoogenboom et al., "Tuning Solution Polymer Properties by Binary Water-Ethanol Solvent Mixtures," Soft Matter, 2008, No. 4(1), pp. 103–107.

[0012] As further described herein, 2-stearyl-2-oxazoline (SteO x ) and 2-ethyl-2-oxazoline (EtO xBrush arm copolymers (and even some linear homopolymers) of 2-oxazoline monomers, as well as other oxazoline monomers, were synthesized by living CROP, yielding several well-defined polymers with different polarities and oil solubility. Grafted brush copolymers having a methacrylate-(2-ethylhexyl) methacrylate random copolymer skeleton (poly(xMA)) obtained by RAFT polymerization were reacted with brush arm copolymer side chains (polyOx) using the graft-ont method. The solubility behavior of 2-oxazoline copolymers and grafted brush copolymers in commercially available oils (e.g., Yubase® 4) was evaluated by turbidity measurement and thermal analysis. This is considered to be the first example of thermally responsive linear copolymers and grafted brush copolymers based on 2-oxazoline and methacrylate monomers that exhibit UCST-type phase transitions in pure non-aqueous systems. The disclosure also provides the use of brush copolymer compositions according to the disclosure for modifying the turbidity, thermal, and / or viscosity properties of lubricant compositions. [Modes for carrying out the invention]

[0013] This disclosure relates to brush copolymers, methods for producing the same, and their applications / uses, for example, as lubricant components and / or in lubricant compositions. The brush copolymers disclosed herein have a copolymer skeleton and copolymer brush arms. Each copolymer brush arm contains, or is made to consist of, at least two different monomer repeating units of acylated poly(alkyleneamine) of the following formulas (1) and (2). [ka] In equations (1) and (2), each R 5 Each is a hydrogen atom or a linear or branched C1-C atom. 24 Alkyl moiety (especially linear or branched C2-C) 18 The alkyl portion may also be, and each R 6 Each R 5is different, but the number of carbon atoms in each R 5 is the same as or more than that, each individually being a straight-chain or branched C8-C 24 alkyl moiety (in particular, a straight-chain or branched C8-C 20 alkyl moiety). In these formulas, the subscript letters y and z may each be 1 or 2 (in particular, it is possible for both subscript letters y and z to be 1). Due to the typical similarity (but not identity) between the monomer repeating units of formulas (1) and (2), the brush arms may be a random (or nearly random) copolymer, but in any case are not block copolymers, and typically the block copolymer characteristics are considered not to be high.

[0014] As used herein, the term "alkyl" with respect to hydrocarbons should be understood to distinguish non-aromatic and heteroatom-free hydrocarbons from both aromatic hydrocarbons and heteroatom-containing hydrocarbons. Thus, the term "alkyl" may be defined to include cycloalkyl groups, alkenyl groups having one or more carbon-carbon double bonds (in addition to any cyclic group, or excluding such cyclic group; also including conjugated double bonds as long as the conjugation does not form an aromatic conjugation), and alkynyl groups having one or more carbon-carbon triple bonds (in addition to any carbon-carbon double bonds and / or any cyclic groups, or excluding them). As is known to those skilled in the art, in hydrocarbon-based materials, "heteroatom" represents an atom other than hydrogen and carbon, which includes oxygen, nitrogen, sulfur, phosphorus, selenium, halogen, metalloids (boron, silicon, germanium, arsenic, antimony, tellurium, etc.), metals (alkali metals, alkaline earth metals, transition metals, lanthanides, actinides, aluminum, gallium, indium, lead, tin, bismuth, etc.), and noble gases, but is not necessarily limited thereto. However, in some embodiments, the term "alkyl" may be limited to only acyclic single-chain carbon-carbon bond hydrocarbons.

[0015] 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 contains monomers of formulas (1) and (2), or is basically composed of those monomers, the sum of m + n represents 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%~85 mol%, 70 mol%~80 mol%, 80 mol%~100 mol%, 80 mol%~99 mol%, 80 mol%~95 mol%, 80 mol%~90 mol%, 90 mol%~100 mol%, 90 mol%~99 mol%, 90 mol%~95 mol%, 95 mol%~100 mol%, 95 mol%~99 mol%, or 99 mol%~100 mol%; in particular, 90 mol%~100 mol%, 95 mol%~100 mol%, or 99 mol%~100 mol%). Additionally or alternatively, the average degree of polymerization of the brush arms 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 arms and / or the sum of m+n may 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 arms and / or the sum of m+n may be 75 or less, 60 or less, 11 to 75, or 14 to 60). Additionally or alternatively, brush arms may be characterized by a ratio of the subscript m:n; for example, the ratio m:n may be 1:99~9:1, 1:49~4:1, 1:25~2:1, 1:19~1.5:1, 1:14~1:1, or 1:9~1:1.5 (especially 1:25~2:1, 1:19~1.5:1, 1:14~1:1, or 1:9~1:1.5).

[0016] Each copolymer skeleton may contain, or be composed of, monomer repeating units of at least two different acrylate monomers of the following formulas (3) and (4). [ka] In equations (3) and (4), each R 1 and R 3 Each R may be a hydrogen atom, a linear or branched C1-C4 alkyl moiety, or a mixture thereof (in particular, hydrogen, methyl, and / or ethyl); each R 2 Each R may individually be a covalent copolymer brush arm, residual hydrogen, or a residual trisubstituted silyl group, and these substituents may individually be a linear, branched, and / or cyclic C1-C8 alkyl, aryl, alkaryl, or aralkyl 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 (in particular, a covalent copolymer brush arm, residual hydrogen, a residual linear or branched C2-C4 hydroxyalkyl moiety, or a residual monovalent counterion); and each R 4 These are individually linear, branched, and / or cyclic C8-C 30 Alkyl, aryl, alkalyl, or aralkyl moieties (especially linear or branched C8-C) 22 The alkyl portion may also be present. In certain embodiments, the brush copolymer composition comprises a copolymer backbone, where 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 R 2 The base is a covalent copolymer brush arm. In certain embodiments, the copolymer backbone may be a random (or nearly random) copolymer, but in any case it is not a block copolymer and is typically not considered to have high block copolymer properties.

[0017] If a residual monovalent counterion is present, it is advantageous that the counterion be a monovalent cation. In some embodiments, the residual monovalent counterion may include, basically consist of, or be composed of, metal ions such as lithium, potassium, sodium, copper(I), silver(I), etc., or combinations thereof; nonmetal ions such as ammonium; or mixtures thereof. In embodiments where the copolymer skeleton consists only of monomers of formulas (1) and (2), the sum of the subscripts a and b naturally represents 100 mol% of the average degree of polymerization of the copolymer skeleton. However, in embodiments where the copolymer skeleton contains monomers of formulas (1) and (2), or basically consists of those monomers, the sum of a + b represents 60 mol% to 100 mol% of the average degree of polymerization of the copolymer skeleton (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%; in particular, 90 mol% to 100 mol%, 95 mol% to 100 mol%, or 99 mol% to 100 mol%) may also be used.

[0018] Additionally or alternatively, the average degree of polymerization of the copolymer skeleton 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 skeleton and / or the sum of a+b may 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 skeleton and / or the sum of a+b may be 400 or less, 250 or less, 20 to 250, or 25 to 200). Additionally or alternatively, copolymer skeletons may be characterized by a subscript a:b ratio; for example, the ratio a:b may be 1:19–1:1.5, 1:14–1:2, 1:9–1:2.5, 1:7–1:3, 1:6–1:3.5, or approximately 1:4 (particularly 1:19–1:1.5, 1:7–1:3, or 1:6–1:3.5). Brush copolymer compositions and their respective reactants / intermediate products can be formed by a number of different methods. Specific methods and materials are disclosed herein. However, identical or similar brush copolymer composition products may be obtained using other methods and / or materials.

[0019] For example, copolymer brush arms can be produced by polymerizing at least two different cyclic monomers that, when polymerized, will form repeating units of formulas (1) and (2), respectively. Examples of such monomers include 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-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 Xazoline, 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-tridecyl-2-oxazoline, 2-tetradecyl-2-oxazoline, 2-pentadecyl-2-oxazoline, 2-pentadecenyl-2-oxazoline, 2-hexadecyl-2-oxazoline, 2-heptadecyl-2-oxazoline, 2-(methylhexadecyl)-2-oxazoline Xazoline, 2-heptadecenyl-2-oxazoline, 2-heptadecadienyl-2-oxazoline, 2-heptadecatriaenyl-2-oxazoline, 2-heptadecatetetraenyl-2-oxazoline, 2-octadecyl-2-oxazoline, 2-nonadecyl-2-oxazoline, 2-nonadecenyl-2-oxazoline, 2-nonadecatecadienyl-2-oxazoline, 2-nonadecatetetraenyl-2-oxazoline, 2-nonadecapentaenyl-2-oxazoline,2-Eicosanyl-2-oxazoline, 2-Heneicosanyl-2-oxazoline, 2-Docosanyl-2-oxazoline, 2-Tricosanyl-2-oxazoline, 2-Tetracosanyl-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-Propenyl-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-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-Di Hydro-1,3-oxazine, 2-(methylpentyl)-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-(methylhexyl)-4,5-dihydro-1,3-oxazine, 2-(dimethylpentyl)-4,5-dihydro-1,3-oxazine Sazine, 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-Pentadecyl-4,5-dihydro-1,3-oxazine, 2-Pentadecenyl-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 Zin, 2-heptadecenyl-4,5-dihydro-1,3-oxazine, 2-heptadecadienyl-4,5-dihydro-1,3-oxazine, 2-heptadecatetrienyl-4,5-dihydro-1,3-oxazine, 2-heptadecatetetraenyl-4,5-dihydro-1,3-oxazine, 2-octadecyl-4,5-dihydro-1,3-oxazine, 2-nonadecyl-4,5-dihydro Examples include, but are not limited to, -1,3-oxazine, 2-nonadecenyl-4,5-dihydro-1,3-oxazine, 2-nonadecadienyl-4,5-dihydro-1,3-oxazine, 2-nonadecatriaenyl-4,5-dihydro-1,3-oxazine, 2-nonadecatetraenyl-4,5-dihydro-1,3-oxazine, 2-nonadecapentaeenyl-4,5-dihydro-1,3-oxazine, 2-eicosanyl-4,5-dihydro-1,3-oxazine, 2-henicosanyl-4,5-dihydro-1,3-oxazine, 2-docosanyl-4,5-dihydro-1,3-oxazine, 2-tricosanyl-4,5-dihydro-1,3-oxazine, 2-tetracosanyl-4,5-dihydro-1,3-oxazine, and combinations thereof.

[0020] When copolymerizing at least two different (hetero)cyclic monomers (e.g., oxazoline and / or oxazine as defined herein, each containing a nitrogen atom and an oxygen atom), brush arms can be advantageously formed by cationic ring-opening polymerization (CROP). Radical schemes, anionic schemes, or other polymerization schemes are not excluded for (hetero)cyclic monomers such as oxazoline / oxazine, but cationic methods make the oxazolinium / oxazinium (hetero)cyclic cation relatively stable at the polymerizable chain ends. As those skilled in the art will understand, suitable CROP initiators include, but are not limited to, electrophilic sulfonic acid esters such as alkyl tosylates (e.g., methyl tosylate), alkyl nosylates, alkyl brosylates, alkyl trifluates, oxazinium salts, oxazolinium salts, alkyl halides, Lewis acids containing relatively stable anions, and other functional compounds with sufficiently low (e.g., almost no) nucleophilicity, as well as combinations or mixtures thereof. For example, to achieve relatively efficient initiation / progress while reducing or eliminating undesirable termination reactions and / or side reactions, a suitable (co)polymerization temperature can be selected based on the choice of monomer(s) and initiator.

[0021] While suitable initiators may be diluted with appropriate solvents, CROP polymerization can advantageously be carried out in relatively low concentrations of solvent, for example, in bulk amounts (in this specification, a small amount of initiator solvent added to the monomer reactant system is still considered a "bulk amount" relative to the amounts of at least two monomers and any other polymerization reactants / accelerators, as any initiator solvent is typically present in trace amounts). In fact, if the polymerization chain ends are sufficiently stable, living polymerization or pseudo-living polymerization is possible, which usually allows for better control of molecular weight, molecular weight distribution, reduction of side reactions, etc., and thus usually results in the formation of more uniform and chemically stable brush copolymer arms. Living polymerization or pseudo-living polymerization may further offer the advantage of copolymer brush arms, which can be grafted onto sites on the copolymer backbone with little or no activation or post-polymerization functionalization.

[0022] Alternatively, at least one (some) or both (all) of the monomers polymerized to form at least two different repeating units can be acyclic. In one such example, a single acyclic monomer can be used to polymerize a homopolymer poly(alkyleneamine) chain (e.g., poly(ethyleneamine) or poly(propyleneamine)) in another manner, and then a postpolymerization reaction acylates the secondary amine skeleton with at least two different acyl groups to form copolymer brush arms having repeating units of formulas (1) and (2). In another such example, it is possible to use at least two different monomers (one / some, or both / all) to copolymerize an intermediate copolymer having alkyleneamine and / or functionalized alkyleneamine repeating units, and then subject one or both of the pendant groups on the skeletal nitrogen of each repeating unit (one or more) formed by the copolymerization to a post-polymerization reaction, in which their nitrogens are selectively acylated with appropriate acyl groups (one or more) to form copolymer brush arms having repeating units of formulas (1) and (2).

[0023] In similar but alternative embodiments, both (all) of the monomers polymerized to form at least two different repeating units may be cyclic to increase susceptibility to ring-opening polymerization. However, one (some) or both (all) of the monomers may form an intermediate polymer or copolymer, and one (some) or both (all) of the functional groups on the skeletal nitrogen may be R as described in formulas (1) and (2). 5 -C(=O)- and R 6 The choice of group may be made to create a situation different from that of the -C(=O)-acyl group. Subsequently, one or both of the pendant groups on the nitrogen skeleton of each repeating unit (one or more) may be subjected to the post-polymerization reaction, and those nitrogens may be selectively acylated with the appropriate acyl group (one or more).

[0024] The copolymer skeleton can be formed by polymerizing at least two different acrylate monomers that, when polymerized, form repeating units of formulas (3) and (4), respectively. Examples of monomers that can polymerize to form repeating units of formula (3) include acrylic acid, methacrylic acid, ethacrylic acid, trimethylsilyl acrylate, trimethylsilyl methacrylate, ethyldimethylsilyl acrylate, ethyldimethylsilyl methacrylate, phenyldimethylsilyl acrylate, phenyldimethylsilyl acrylate, methyldiphenylsilyl acrylate, methyldiphenylsilyl methacrylate, tolyldimethylsilyl acrylate, tolyldimethylsilyl methacrylate, benzyldimethylsilyl acrylate, benzyldimethylsilyl methacrylate, triphenylsilyl acrylate, triphenylsilyl methacrylate, acrylic anhydride, methacrylic anhydride, ethacrylacetic anhydride, acrylpropionic anhydride, methacrylic propionic anhydride, ethacrylpropionic anhydride, acrylbutyric anhydride, ethacrylbutyric anhydride, and acryloisobutyric anhydride. Methacrylisobutyric anhydride, ethacrylisobutyric anhydride, acrylpentanoic acid anhydride, methacrylpentanoic acid anhydride, ethacrylpentanoic acid anhydride, acrylmethylbutanoic acid anhydride, ethacrylmethylbutanoic acid anhydride, acrylpivalic acid anhydride, ethacrylpivalic acid anhydride, acrylhexanoic acid anhydride, ethacrylhexanoic acid anhydride, ethacrylmethylpentanoic acid anhydride, ethacrylmethylpentanoic acid anhydride, acryldimethylbutanoic acid anhydride Acrylic acid anhydride, methacrylatedimethylbutane anhydride, ethacrylatedimethylbutanoic acid anhydride, acrylheptanoic acid anhydride, methacrylateheptanoic acid anhydride, ethacrylateheptanoic acid anhydride, acrylmethylhexanoic acid anhydride, ethacrylatemethylhexanoic acid anhydride, acryldimethylpentanoic acid anhydride, ethacrylatedimethylpentanoic acid anhydride, acrylethylpentanoic acid anhydride, ethacrylateethylpentanoic acid anhydride, acrylcyclohexanecarboxylic acid anhydride,Methacryliccyclohexanecarboxylic acid anhydride, ethacrylcyclohexanecarboxylic acid anhydride, acrylicbenzoic acid anhydride, methacrylbenzoic acid anhydride, ethacrylbenzoic acid anhydride, 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(I) acrylate, copper(I) methacrylate, silver(I) acrylate, silver(I) methacrylate, ammonium acrylate, ammonium methacrylate, alkylated ammonium ( Examples of acrylates (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 acrylate, triethylammonium methacrylate, tetraethylammonium acrylate, tetraethylammonium methacrylate, etc., or mixtures thereof) or combinations thereof are listed, but are not necessarily limited to these.

[0025] Examples of monomers that can polymerize to form the repeating unit of formula (4) include octyl acrylate, octyl methacrylate, methylheptyl acrylate, methylheptyl methacrylate, ethylhexyl methacrylate, dimethylhexyl acrylate, dimethylhexyl methacrylate, trimethylpentyl acrylate, trimethylpentyl methacrylate, methylethylpentyl acrylate, methylethylpentyl methacrylate, propylpentyl acrylate, propylpentyl methacrylate, cyclooctyl acrylate, and Chlooctyl methacrylate, cycloheptyl methyl acrylate, cycloheptyl methyl methacrylate, tricyclo[3.3.0.0]octanyl acrylate, tricyclo[3.3.0.0]octanyl methacrylate, tricyclo[2.2.1.1]octanyl acrylate, tricyclo[2.2.1.1]octanyl methacrylate, bicyclo[2.2.2]octanyl acrylate, bicyclo[2.2.2]octanyl methacrylate, bicyclo[3.2.1]octanyl acrylate, bicyclo[3.2.1]octanyl methacrylate Octahydropentalenyl acrylate, octahydropentalenyl methacrylate, methylcycloheptyl acrylate, methylcycloheptyl methacrylate, cycloheptyl methyl acrylate, cycloheptyl methyl methacrylate, cyclohexyl ethyl acrylate, cyclohexyl ethyl methacrylate, ethylcyclohexyl acrylate, ethylcyclohexyl methacrylate, dimethylcyclohexyl acrylate, dimethylcyclohexyl methacrylate, methylcyclohexyl methyl acrylate, methylcyclohexyl methyl methacrylate, cyclopentyl propyl acrylate, propylcyclopentyl methacrylate, methylcyclopentyl ethyl acrylate, methylcyclopentyl ethyl methacrylate, dimethylcyclopentyl methyl acrylate, dimethylcyclopentyl methyl methacrylate, ethylcyclopentyl methyl acrylate, ethylcyclopentyl methyl methacrylate, trimethylcyclopentyl acrylate, trimethylcyclopentyl methacrylate,Methyl ethyl cyclopentyl acrylate, methyl ethyl cyclopentyl methacrylate, pentarenyl acrylate, pentarenyl methacrylate, methyl benzyl acrylate, methyl benzyl methacrylate, benzyl methyl acrylate, benzyl methyl methacrylate, dimethylphenyl acrylate, dimethylphenyl methacrylate, ethylphenyl acrylate, ethylphenyl methacrylate, phenyl ethyl acrylate, phenyl ethyl methacrylate, nonyl acrylate, nonyl methacrylate, methyl octyl acrylate Methyl octyl methacrylate, ethylheptyl acrylate, ethylheptyl methacrylate, dimethylheptyl acrylate, dimethylheptyl methacrylate, trimethylhexyl acrylate, trimethylhexyl methacrylate, methyl ethylhexyl acrylate, methyl ethylhexyl methacrylate, propylhexyl acrylate, propylhexyl methacrylate, tetramethylpentyl acrylate, tetramethylpentyl methacrylate, ethyldimethylpentyl acrylate, ethyldimethylpentyl methacrylate, ethyl methylpentyl methacrylate, methyl methyl Lupentyl acrylate, diethylpentyl methacrylate, tricyclo[4.3.0.0]nonanyl acrylate, tricyclo[4.3.0.0]nonanyl methacrylate, bicyclo[3.2.2]nonanyl acrylate, bicyclo[3.2.2]nonanyl methacrylate, bicyclo[3.3.1]nonanyl acrylate, bicyclo[3.3.1]nonanyl methacrylate, bicyclo[4.2.1]nonanyl acrylate, bicyclo[4.2.1]nonanyl methacrylate, octahydroindenyl acrylate, octahydroindenyl methacrylate T, cyclooctyl methyl acrylate, cyclooctyl methyl methacrylate, methylcyclooctyl acrylate, methylcyclooctyl methacrylate, octahydropentalenyl methyl acrylate, octahydropentalenyl methyl methacrylate, methyl octahydropentalenyl acrylate, methyl octahydropentalenyl methacrylate, ethylcycloheptyl acrylate, ethylcycloheptyl methacrylate, cycloheptyl ethyl acrylate, cycloheptyl ethyl methacrylate, dimethylcycloheptyl acrylate,Dimethylcycloheptyl methacrylate, methylcycloheptyl methyl acrylate, methylcycloheptyl methyl methacrylate, cyclohexyl propyl acrylate, cyclohexyl propyl methacrylate, propylcyclohexyl acrylate, propylcyclohexyl methacrylate, methyl ethylcyclohexyl acrylate, methyl ethylcyclohexyl methacrylate, methylcyclohexyl acrylate, methylcyclohexyl ethyl methacrylate, ethylcyclohexyl methyl acrylate, ethylcyclohexyl methyl methacrylate, trimethylcyclohexyl acrylate, trimethylcyclohexyl Methacrylate, dimethylcyclohexylmethyl acrylate, dimethylcyclohexylmethyl methacrylate, cyclopentyl butyl acrylate, cyclopentyl butyl methacrylate, butylcyclopentyl acrylate, butylcyclopentyl methacrylate, methylcyclopentyl propyl acrylate, methylcyclopentyl propyl methacrylate, propylcyclopentyl methyl acrylate, propylcyclopentyl methyl methacrylate, diethylcyclopropyl acrylate, diethylcyclopentyl methacrylate, ethylcyclopentyl ethyl acrylate, ethylcyclopentyl ethyl methacrylate, Dimethylcyclopentyl ethyl acrylate, dimethylcyclopentyl ethyl methacrylate, tetramethylcyclopentyl acrylate, tetramethylcyclopentyl methacrylate, trimethylcyclopentyl methyl acrylate, trimethylcyclopentyl methyl methacrylate, indenyl acrylate, indenyl methacrylate, spiro[4.4]nonanyl acrylate, spiro[4.4]nonanyl methacrylate, spiro[4.4]nonadienyl acrylate, spiro[4.4]nonadienyl methacrylate, spiro[4.4]nonatetraenyl acrylate, spiro[4.4] Nonatetraenyl methacrylate, methylphenyl ethyl methacrylate, methylpentalenyl acrylate, methylpentalenyl methacrylate, pentarenyl methyl acrylate, pentarenyl methyl methacrylate, ethyl benzyl acrylate, ethyl benzyl methacrylate, benzyl ethyl acrylate, benzyl ethyl methacrylate, dimethyl benzyl acrylate, dimethyl benzyl methacrylate, phenyl propyl acrylate, phenyl propyl methacrylate, propyl phenyl acrylate, propyl phenyl methacrylate, trimethylphenyl acrylate, trimethylphenyl methacrylate, methyl ethyl phenyl acrylate, methyl ethyl phenyl methacrylate, methylphenyl ethyl acrylate, decyl acrylate, decyl methacrylate, methyl nonyl acrylate, methyl nonyl methacrylate, ethyl octyl acrylate, ethyl octyl methacrylate, dimethyl octyl acrylate, dimethyl octyl methacrylate, propylheptyl acrylate, propylheptyl methacrylate, methyl Tylheptyl acrylate, methylethylheptyl methacrylate, trimethylheptyl acrylate, trimethylheptyl methacrylate, butylhexyl acrylate, butylhexyl methacrylate, tetramethylhexyl acrylate, tetramethylhexyl methacrylate, dimethylethylhexyl acrylate, dimethylethylhexyl methacrylate, diethylhexyl acrylate, diethylhexyl methacrylate, pentamethylpentyl acrylate, pentamethylpentyl methacrylate, ethyltrimethylpentyl Tyl(ethyltrmethylpentyl) acrylate, ethyltrimethylpentyl methacrylate, diethylmethylpentyl acrylate, diethylmethylpentyl methacrylate, butylmethylpentyl acrylate, butylmethylpentyl methacrylate, ethylpropylpentyl acrylate, ethylpropylpentyl methacrylate, dimethylpropylpentyl acrylate, dimethylpropylpentyl methacrylate, tetracyclo[4.2.1.1.0]decanyl acrylate, tetracyclo[4.2.1.1.0] Decanyl methacrylate, adamantanyl acrylate, adamantanyl methacrylate, decahydrocyclopentapentarenyl acrylate, decahydrocyclopentapentarenyl methacrylate, . Tricyclo[4.4.0.0]decanyl acrylate, tricyclo[4.4.0.0]decanyl methacrylate, tricyclo[4.2.1.1]decanyl acrylate, tricyclo[4.2.1.1]decanyl methacrylate, tricyclo[3.3.1.1]decanyl acrylate, tricyclo[3.3.1.1]decanyl methacrylate, tricyclo[2.2.2.2]decanyl acrylate, tricyclo[2.2.2.2]decanyl methacrylate, bicyclo[3.3.2]decanyl acrylate, bicyclo[3.3.2]decanyl methacrylate T, bicyclo[4.2.2]decanyl acrylate, bicyclo[4.2.2]decanyl methacrylate, decahydronaphthalenyl acrylate, decahydronaphthalenyl methacrylate, decahydroazlenyl acrylate, decahydroazlenyl methacrylate, methyl octahydroindenyl acrylate, methyl octahydroindenyl methacrylate, octahydroindenyl methyl acrylate, octahydroindenyl methyl methacrylate, octahydropentanyl ethyl acrylate, octahydropentanyl ethyl methacrylate Ethyl octahydropentalenyl acrylate, ethyl octahydropentalenyl methacrylate, methyl octahydropentalenyl methyl acrylate, methyl octahydropentalenyl methyl methacrylate, dimethyl octahydropentalenyl acrylate, dimethyl octahydropentalenyl methacrylate, dimethylcyclooctyl acrylate, dimethylcyclooctyl methacrylate, methylcyclooctyl methyl acrylate, methylcyclooctyl methyl methacrylate, ethylcyclooctyl acrylate, ethylcyclooctyl Tyl methacrylate, propylcycloheptyl acrylate, propylcycloheptyl methacrylate, cycloheptyl propyl acrylate, cycloheptyl propyl methacrylate, ethylcycloheptyl methyl acrylate, ethylcycloheptyl methyl methacrylate, methylcycloheptyl ethyl acrylate, methylcycloheptyl ethyl acrylate, trimethylcycloheptyl acrylate, trimethylcycloheptyl methacrylate, dimethylcycloheptyl methyl acrylate, dimethylcycloheptyl methyl methacrylate,Cyclohexyl butyl acrylate, cyclohexyl butyl methacrylate, butyl cyclohexyl acrylate, butyl cyclohexyl methacrylate, propyl cyclohexyl methyl acrylate, propyl cyclohexyl methyl methacrylate, methyl propyl cyclohexyl acrylate, methyl propyl cyclohexyl methacrylate, methyl cyclohexyl propyl acrylate, methyl cyclohexyl propyl methacrylate, ethyl cyclohexyl acrylate, ethyl cyclohexyl ethyl methacrylate, diethyl cyclohexyl acrylate, diethyl cyclohexyl methacrylate, dimethyl cyclohexyl ethyl acrylate, dimethyl cyclohexyl methacrylate, tetramethyl cyclohexyl acrylate, tetramethyl cyclohexyl methacrylate, trimethylcyclohexyl methyl acrylate, trimethylcyclohexyl methyl methacrylate, naphthalenyl acrylate, naphthalenyl methacrylate Tetrahydronaphthalenyl acrylate, tetrahydronaphthalenyl methacrylate, bicyclopentadienyl acrylate, bicyclopentadienyl methacrylate, azurenyl acrylate, azurenyl methacrylate, dimethylpentalenyl acrylate, dimethylpentalenyl methacrylate, methylpentalenyl methyl acrylate, methylpentalenyl methyl methacrylate, ethylpentalenyl acrylate, ethylpentalenyl methacrylate, pentarenyl ethyl acrylate, pentarenyl methacrylate, spiro[4.5]decanyl acrylate, spiro[4.5]decanyl methacrylate, spiro[4.5]decadienyl acrylate, spiro[4.5]decadienyl methacrylate, spiro[4.5]decatetraenyl acrylate, spiro[4.5]decatetraenyl methacrylate, butylphenyl acrylate, butylphenyl methacrylate, phenylbutyl acrylate, phenylbutyl methacrylate, Propylbenzyl acrylate, propylbenzyl methacrylate, benzyl propyl acrylate, benzyl propyl methacrylate, 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 methacrylate, ethyl nonyl acrylate, ethyl nonyl methacrylate, dimethyl nonyl acrylate, dimethyl nonyl methacrylate, propyl octyl acrylate, propyl octyl methacrylate, methylethyl octyl acrylate, methylethyl octyl methacrylate, trimethyl octyl acrylate, trimethyl octyl methacrylate, butylheptyl acrylate, butylheptyl methacrylate, methylpropylheptyl acrylate, methylpropylheptyl methacrylate Diethylheptyl acrylate, diethylheptyl methacrylate, tetramethylheptyl acrylate, tetramethylheptyl methacrylate, pentylhexyl acrylate, pentylhexyl methacrylate, pentamethylhexyl acrylate, pentamethylhexyl methacrylate, trimethylethylhexyl acrylate, trimethylethylhexyl methacrylate, methyldiethylhexyl acrylate, methyldiethylhexyl methacrylate, propylethylhexyl acrylate , propyl ethylhexyl methacrylate, propyl dimethylhexyl acrylate, propyl dimethylhexyl methacrylate, tetracyclo[3.3.1.1.1]undecanyl acrylate, tetracyclo[3.3.1.1.1]undecanyl methacrylate, tetracyclo[6.2.1.0.0]undecanyl acrylate, tetracyclo[6.2.1.0.0]undecanyl methacrylate, tetracyclo[5.3.1.0.0]undecanyl acrylate, tetracyclo[5.3.1.0.0] Undecanyl methacrylate, methyl adamantanyl acrylate, methyl adamantanyl methacrylate, adamantanyl methyl acrylate, adamantanyl methyl methacrylate, tricyclo[5.2.1.1]undecanyl acrylate, tricyclo[5.2.1.1]undecanyl methacrylate, tricyclo[4.3.1.1]undecanyl acrylate, tricyclo[4.3.1.1]undecanyl methacrylate, tricyclo[4.2.2.1]undecanyl acrylate, tricyclo[ 4.2.2.1] Undecanyl methacrylate, tricyclo[3.3.2.1] Undecanyl acrylate, tricyclo[3.3.2.1] Undecanyl methacrylate, tricyclo[3.2.2.2] Undecanyl acrylate, tricyclo[3.2.2.2] Undecanyl methacrylate, bicyclo[4.3.2] Undecanyl acrylate, bicyclo[4.3.2] Undecanyl methacrylate, bicyclo[4.4.1] Undecanyl acrylate, bicyclo[4.4.1] Undecanyl methacrylate, Bicyclo[3.3.3]undecanyl acrylate, Bicyclo[3.3.3]undecanyl methacrylate, Bicyclo[5.3.1]undecanyl acrylate, Bicyclo[5.3.1]undecanyl methacrylate, Bicyclo[5.2.2]undecanyl acrylate, Bicyclo[5.2.2]undecanyl methacrylate, Bicyclo[6.2.1]undecanyl acrylate, Bicyclo[6.2.1]undecanyl methacrylate, Bicyclo[7.1.1]undecanyl acrylate, Bicyclo[7.1. 1] Undecanyl methacrylate, methyl decahydronaphthalenyl acrylate, methyl decahydronaphthalenyl methacrylate, decahydronaphthalenyl methyl acrylate, decahydronaphthalenyl methyl methacrylate, methyl decahydroazlenyl acrylate, methyl decahydroazlenyl methacrylate, decahydroazlenyl methyl acrylate, decahydroazlenyl methyl methacrylate, dimethyl octahydroindenyl acrylate, dimethyl octahydroindenyl methacrylate, . Ethyl octahydroindenyl acrylate, ethyl octahydroindenyl methacrylate, octahydroindenyl ethyl acrylate, octahydroindenyl ethyl methacrylate, octahydropentarenyl propyl acrylate, octahydropentanyl propyl methacrylate, propyl octahydropentarenyl acrylate, propyl octahydropentarenyl methacrylate, trimethylcyclooctyl acrylate, trimethylcyclooctyl methacrylate, dimethylcyclooctyl methyl acrylate, dimethylcyclooctyl methyl methacrylate, ethylcyclooctyl methyl acrylate, ethylcyclooctyl methyl methacrylate, butylcycloheptyl acrylate, butylcycloheptyl methacrylate, cycloheptyl butyl acrylate, cycloheptyl butyl methacrylate, diethylcycloheptyl acrylate, diethylcycloheptyl methacrylate, tetramethylcycloheptyl acrylate Tetramethylcycloheptyl methacrylate, cyclohexylpentyl acrylate, cyclohexylpentyl methacrylate, pentylcyclohexyl acrylate, pentylcyclohexyl methacrylate, pentamethylcyclohexyl acrylate, pentamethylcyclohexyl methacrylate, cyclopentapentarenyl acrylate, cyclopentapentarenyl acrylate, cyclopentadienylphenyl acrylate, cyclopentadienyl methacrylate , phenylcyclopentadienyl acrylate, phenylcyclopentadienyl methacrylate, spiro[4.6]undecanyl acrylate, spiro[4.6]undecanyl methacrylate, spiro[4.6]undecadienyl acrylate, spiro[4.6]undecadienyl methacrylate, spiro[4.6]undecatrienyle acrylate, spiro[4.6]undecatrienyle methacrylate, spiro[4.6]undecapentenyl acrylate, spiro[4.6] Undecapentaenyl methacrylate, methylnaphthalenyl acrylate, methylnaphthalenyl methacrylate, naphthalenyl methyl acrylate, naphthalenyl methyl methacrylate, methylbicyclopentadienyl indenyl acrylate, methylbicyclopentadienyl idenyl methacrylate, methylazlenyl acrylate, methylazlenyl methacrylate, azulenyl methyl acrylate, azulenyl methyl methacrylate, methyltetrahydronaphthalenyl Syl acrylate, methyltetrahydronaphthalenyl methacrylate, spiro[5.5]undecany acrylate, spiro[5.5]undecany methacrylate, diethylbenzyl acrylate, diethylbenzyl methacrylate, pentamethylphenyl acrylate, pentamethylphenyl methacrylate, phenylpentyl acrylate, phenylpentyl methacrylate, dodecyl acrylate, dodecyl methacrylate, methylundecyl acrylate, methylundecyl methacrylate, ethyldecyl acrylate, ethyldecyl methacrylate Crilate, dimethyldecyl acrylate, dimethyldecyl 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 methacrylate Tyloctyl methacrylate, pentylheptyl acrylate, pentylheptyl methacrylate, pentamethylheptyl acrylate, pentamethylheptyl methacrylate, trimethylethylheptyl acrylate, trimethylethylheptyl methacrylate, methyldiethylheptyl acrylate, methyldiethylheptyl methacrylate, propylethylheptyl acrylate, propylethylheptyl methacrylate, propyldimethylheptyl acrylate, propyldimethylheptyl methacrylate, tetracyclo[7.2.1.0.0] Dodecanyl acrylate, tetracyclo[7.2.1.0.0] dodecanyl methacrylate, tetracyclo[4.2.2.1.1] dodecanyl acrylate, tetracyclo[4.2.2.1.1] dodecanyl methacrylate, tetracyclo[4.3.1.1.1] dodecanyl acrylate, tetracyclo[4.3.1.1.1] dodecanyl methacrylate, tetracyclo[3.3.2.1.1] dodecanyl acrylate, tetracyclo[3.3.2.1.1] dodecanyl methacrylate, ethyl adamantyl acrylate, ethyl adamantyl methacrylate, dimethyl adamantanyl acrylate, dimethyl adamantanyl methacrylate, adamantanyl ethyl acrylate, adamantanyl ethyl methacrylate, tricyclo[6.2.1.1] dodecanyl acrylate, tricyclo[6. 2.1.1] Dodecanyl methacrylate, tricyclo[5.3.1.1] dodecanyl acrylate, tricyclo[5.3.1.1] dodecanyl methacrylate, tricyclo[4.4.1.1] dodecanyl acrylate, tricyclo[4.4.1.1] dodecanyl methacrylate, tricyclo[5.2.2.1] dodecanyl acrylate, tricyclo[5.2.2.1] dodecanyl methacrylate, tri Cyclo[4.3.2.1]dodecanyl acrylate, tricyclo[4.3.2.1]dodecanyl methacrylate, tricyclo[4.2.2.2]dodecanyl acrylate, tricyclo[4.2.2.2]dodecanyl methacrylate, tricyclo[3.3.2.2]dodecanyl acrylate, tricyclo[3.3.2.2]dodecanyl methacrylate, bicyclo[4.3.3]dodecanyl acrylate, . Bicyclo[4.3.3]dodecanyl methacrylate, Bicyclo[4.4.2]dodecanyl acrylate, Bicyclo[4.4.2]dodecanyl methacrylate, Bicyclo[5.4.1]dodecanyl acrylate, Bicyclo[5.4.1]dodecanyl methacrylate, Bicyclo[5.3.2]dodecanyl acrylate, Bicyclo[5.3.2]dodecanyl methacrylate, Bicyclo[6.2.2]dodecanyl acrylate, Bicyclo[6.2.2]dodecanyl methacrylate, Bicyclo[6.3.1]dodecanyl acrylate, Bicyclo[6.3.1]dodecanyl methacrylate Canyl methacrylate, bicyclo[7.2.1]dodecanyl acrylate, bicyclo[7.2.1]dodecanyl methacrylate, bicyclo[8.1.1]dodecanyl acrylate, bicyclo[8.1.1]dodecanyl methacrylate, ethyl decahydronaphthalenyl acrylate, ethyl decahydronaphthalenyl methacrylate, decahydronaphthalenyl ethyl acrylate, decahydronaphthalenyl ethyl methacrylate, ethyl decahydroazlenyl acrylate, ethyl decahydroazlenyl methacrylate, decahydroazlenyl ethyl acrylate Decahydroazlenyl ethyl methacrylate, trimethyl octahydroindenyl acrylate, trimethyl octahydroindenyl methacrylate, propyl octahydroindenyl acrylate, propyl octahydroindenyl methacrylate, octahydroindenyl propyl acrylate, octahydroindenyl propyl methacrylate, butyl octahydropentarenyl acrylate, butyl octahydropentarenyl methacrylate, tetramethylcyclooctyl acrylate, tetramethylcyclooctyl methacrylate, die Diethylcyclooctyl acrylate, diethylcyclooctyl methacrylate, pentylcycloheptyl acrylate, pentylcycloheptyl methacrylate, cycloheptylpentyl acrylate, cycloheptyl methacrylate, pentamethylcycloheptyl acrylate, pentamethylcycloheptyl methacrylate, cyclohexylhexyl acrylate, cyclohexylhexyl methacrylate, cyclohexylcyclohexyl acrylate, cyclohexylcyclohexyl methacrylate, pentamethylcyclohexylmethyl acrylate,Pentamethylcyclohexylmethyl methacrylate, acenaphtyrenyl acrylate, acenaphtyrenyl methacrylate, acenaphthenyl acrylate, acenaphthenyl methacrylate, biphenylyl acrylate, biphenylyl methacrylate, indacenyl acrylate, indacenyl methacrylate, heptarenylate, heptarenylate, cyclopentadienylidene cycloheptatrienyl acrylate, cyclopentadienylidene cycloheptatrienyl methacrylate Relate, cycloheptatrienylidenecyclopentadienyl acrylate, cycloheptatrienylidenecyclopentadienyl methacrylate, methylcyclopentapentarenyl acrylate, methylcyclopentapentarenyl acrylate, methylcyclopentadienylphenyl acrylate, methylcyclopentadienylphenyl methacrylate, cyclopentadienyl tolyl acrylate, cyclopentadienyl tolyl methacrylate, cyclopentadienyl benzyl acrylate, Cyclopentadienylbenzyl methacrylate, methylphenylcyclopentadienyl acrylate, methylphenylcyclopentadienyl methacrylate, tolylcyclopentadienyl acrylate, tolylcyclopentadienyl methacrylate, spiro[5,6]dodecanyl acrylate, spiro[5,6]dodecanyl methacrylate, spiro[5,6]dodecatrienylate, spiro[5,6]dodecatrienylate methacrylate, dimethylnaphthalenyl acrylate, dimethyl Naphthalenyl methacrylate, ethyl naphthalenyl acrylate, ethyl naphthalenyl methacrylate, naphthalenyl ethyl acrylate, naphthalenyl ethyl methacrylate, dimethylazlenyl acrylate, dimethylazlenyl methacrylate, ethylazlenyl acrylate, ethylazlenyl methacrylate, azurenyl ethyl acrylate, azurenyl ethyl methacrylate, dimethyltetrahydronaphthalenyl acrylate, dimethyltetrahydronaphthalenyl methacrylate, Triethylphenyl acrylate, triethylphenyl methacrylate, phenylhexyl acrylate, phenylhexyl methacrylate, hexylphenyl acrylate, hexylphenyl methacrylate, cyclohexylphenyl acrylate, cyclohexylphenyl methacrylate, phenylcyclohexyl acrylate, phenylcyclohexyl methacrylate, tridecyl acrylate, tridecyl methacrylate, methyl dodecyl acrylate, methyl dodecyl methacrylate, dimethylundecyl acrylate, dimethylun Decyl methacrylate, ethyl undecyl acrylate, ethyl undecyl methacrylate, trimethyl decyl acrylate, trimethyl decyl methacrylate, 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, methyl propyl nonyl acrylate, methyl pro Pyrnonyl methacrylate, pentyl octyl acrylate, pentyl octyl methacrylate, pentamethyl octyl acrylate, pentamethyl octyl methacrylate, trimethylethyl octyl acrylate, trimethylethyl octyl methacrylate, methyl diethyl octyl acrylate, methyl diethyl octyl methacrylate, propyl ethyl octyl acrylate, propyl ethyl octyl methacrylate, propyl dimethyl octyl acrylate, propyl dimethyl octyl methacrylate, triethylheptyl acrylate , triethylheptyl methacrylate, tetracyclo[6.3.2.0.0]tridecanyl acrylate, tetracyclo[6.3.2.0.0]tridecanyl methacrylate, tetracyclo[6.2.1.1.1]tridecanyl acrylate, tetracyclo[6.2.1.1.1]tridecanyl methacrylate, tetracyclo[5.3.1.1.1]tridecanyl acrylate, tetracyclo[5.3.1.1.1]tridecanyl methacrylate, tetracyclo[4.4.1.1.1]tridecanyl acrylate, tetracyclo[4.4.1.1.1] Tridecanyl methacrylate, tetracyclo[4.3.2.1.1]tridecanyl acrylate, tetracyclo[4.3.2.1.1]tridecanyl methacrylate, tetracyclo[4.2.2.2.1]tridecanyl acrylate, tetracyclo[4.2.2.2.1]tridecanyl methacrylate, propyladamantyl acrylate, propyladamantyl methacrylate, trimethyladamantanyl acrylate, trimethyladamantanyl methacrylate, tricyclo[7.2.1. 1] Tridecanyl acrylate, tricyclo[7.2.1.1]tridecanyl methacrylate, tricyclo[6.3.1.1]tridecanyl acrylate, tricyclo[6.3.1.1]tridecanyl methacrylate, tricyclo[6.2.2.1]tridecanyl acrylate, tricyclo[6.2.2.1]tridecanyl methacrylate, tricyclo[5.4.1.1]tridecanyl acrylate, tricyclo[5.4.1.1]tridecanyl methacrylate, tricyclo[5.3.2.1]tride Canyl acrylate, tricyclo[5.3.2.1]tridecanyl methacrylate, tricyclo[5.2.2.2]tridecanyl acrylate, tricyclo[5.2.2.2]tridecanyl methacrylate, tricyclo[4.4.2.1]tridecanyl acrylate, tricyclo[4.4.2.1]tridecanyl methacrylate, tricyclo[4.3.3.1]tridecanyl acrylate, tricyclo[4.3.3.1]tridecanyl methacrylate, tricyclo[4.3.2.2]tridecanyl acrylate acrylate, tricyclo[4.3.2.2]tridecanyl methacrylate, dodecahydrofluorenyl acrylate, dodecahydrofluorenyl methacrylate, dodecahydrophenalenyl acrylate, dodecahydrophenalenyl methacrylate, dodecahydroanurenyl acrylate, dodecahydroanurenyl methacrylate, spiro[6.6]tridecahexaenyl acrylate, spiro[6.6]tridecahexaenyl methacrylate, spiro[6.6]tridecatrienylate, . Spiro[6.6]tridecatrienylate, Spiro[6.6]tridecanyl acrylate, Spiro[6.6]tridecanyl methacrylate, Methyl dodecahydroacenaphtyrenyl acrylate, Methyl dodecahydroacenaphtyrenyl methacrylate, Methyl dodecahydro(s)indacenyl acrylate, Methyl dodecahydro(s)indacenyl methacrylate, Methyl dodecahydroheptarenyl acrylate, Methyl dodecahydroheptarenyl methacrylate, Bicyclo[4.4.3]tridecanyl acrylate, Bicyclo[4.4.3]tridecanyl methacrylate, Bicyclo[5.5.1]tridecanyl acrylate, Bicyclo[5.4 .2] Tridecanyl acrylate, bicyclo[5.4.2] tridecanyl methacrylate, bicyclo[5.3.3] tridecanyl acrylate, bicyclo[5.3.3] tridecanyl methacrylate, bicyclo[6.3.2] tridecanyl acrylate, bicyclo[6.3.2] tridecanyl methacrylate, bicyclo[6.4.1] tridecanyl acrylate, bicyclo[6.4.1] tridecanyl methacrylate, bicyclo[7.2.2] tridecanyl acrylate, bicyclo[7.2.2] tridecanyl methacrylate, bicyclo[7.3.1] tridecanyl acrylate, bicyclo[7.3.1] tridecanyl methacrylate, bicyclo[8.2.1] tridecanyl acrylate, bicyclo[8.2.1] Tridecanyl methacrylate, propyl decahydronaphthalenyl acrylate, propyl decahydronaphthalenyl methacrylate, decahydronaphthalenyl propyl acrylate, decahydronaphthalenyl propyl methacrylate, trimethyl decahydronaphthalenyl acrylate, trimethyl decahydronaphthalenyl methacrylate, propyl decahydroazlenyl acrylate, propyl decahydroazlenyl methacrylate, trimethyl decahydroazlenyl acrylate, trimethyl decahydroazlenyl methacrylate, tetramethyl octahydroindenyl acrylate, tetramethyl octahydroindenyl methacrylate, butyl octahydroindenyl acrylate, butyl octahydroindenyl methacrylate, diethyl octahydroindenyl acrylate, diethyl octahydroindenyl methacrylate, pentyl octahydropentalenyl acrylate, pentyl octahydropentalenyl methacrylate, pentamethylcyclooctyl acrylate, pentamethylcyclooctyl methacrylate Lilate, hexylcycloheptyl acrylate, hexylcycloheptyl methacrylate, hexamethylcycloheptyl acrylate, hexamethylcycloheptyl methacrylate, cyclohexylheptyl acrylate, cyclohexylheptyl methacrylate, cyclohexylcycloheptyl acrylate, cyclohexylcycloheptyl methacrylate, cycloheptylcyclohexyl acrylate, cycloheptylcyclohexyl methacrylate, fluorenyl acrylate, fluorenyl methacrylate Phenalenyl acrylate, phenalenyl methacrylate, anurenyl acrylate, anurenyl methacrylate, methyl acenaphthenyl acrylate, methyl acenaphthenyl methacrylate, acenaphthenyl methyl acrylate, acenaphthenyl methyl methacrylate, methyl acenaphthenyl acrylate, methyl acenaphthenyl methacrylate, acenaphthenyl methyl acrylate, acenaphthenyl methyl methacrylate, methyl biphenylyl acrylate, methyl biphenyl methacrylate. Methyl indacenyl acrylate, methyl indacenyl methacrylate, indacenyl methyl acrylate, indacenyl methyl methacrylate, methylheptarenyl acrylate, methylheptarenyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, methyl tridecyl acrylate, methyl tridecyl methacrylate, dimethyl dodecyl acrylate, dimethyl dodecyl methacrylate, ethyl dodecyl acrylate, ethyl dodecyl methacrylate, trimethyl undecyl acrylate, trimethyl undecyl methacrylate 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, trimethylethyl nonyl acrylate, trimethylethyl 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, Xamethyloctyl acrylate, hexamethyloctyl methacrylate, dimethyldiethyloctyl acrylate, dimethyldiethyloctyl methacrylate, butylethyloctyl acrylate, butylethyloctyl methacrylate, butyldimethyloctyl acrylate, butyldimethyloctyl methacrylate, tetracyclo[6.2.2.1.1]tetradecanyl acrylate, tetracyclo[6.2.2.1.1]tetradecanyl methacrylate, tetracyclo[6.3.1.1.1]tetradecanyl acrylate, tetracyclo[6.3.1.1.1] Tetradecanyl methacrylate, tetracyclo[5.4.1.1.1] Tetradecanyl acrylate, tetracyclo[5.4.1.1.1] Tetradecanyl methacrylate, tetracyclo[5.3.2.1.1] Tetradecanyl acrylate, tetracyclo[5.3.2.1.1] Tetradecanyl methacrylate, tetracyclo[4.4.2.1.1] Tetradecanyl acrylate, tetracyclo[5.2.2.2.1] Tetradecanyl acrylate, tetracyclo[5.2.2.2.1] Tetradecanyl methacrylate, tetracyclo[4. 4.2.1.1] Tetradecanyl methacrylate, Tetracyclo[4.4.2.1.1] Tetradecanyl acrylate, Tetracyclo[4.4.2.1.1] Tetradecanyl methacrylate, Tetracyclo[4.3.2.2.1] Tetradecanyl acrylate, Tetracyclo[4.3.2.2.1] Tetradecanyl methacrylate, Tetracyclo[4.3.3.1.1] Tetradecanyl acrylate, Tetracyclo[4.3.3.1.1] Tetradecanyl methacrylate, Tetradecahydrocyclopentaacenaphtyrenyl acrylate, Tetradecahydro Clopentaacenaphthalenyl methacrylate, tetrahydrocyclopentaacenaphthalenyl acrylate, tetradecahydrocyclopentaacenaphthalenyl methacrylate, tetradecahydrodicyclopentapentarenyl acrylate, tetradecahydrodicyclopentapentarenyl methacrylate, tetradecahydroanthracenyl acrylate, tetradecahydroanthracenyl methacrylate, tetradecahydrophenanthrenyl acrylate, tetradecahydrophenanthrenyl methacrylate, tetradecahydrocycloheptanaphthalenyl acrylate Rate, tetradecahydrocycloheptanaphthalenyl methacrylate, hexahydrocycloheptanaphthalenyl acrylate, hexahydrocycloheptanaphthalenyl methacrylate, tetradecahydrooctalenyl acrylate, tetradecahydrooctalenyl methacrylate, hexahydrooctalenyl acrylate, hexahydrooctalenyl methacrylate, tricyclo[8.2.1.1]tetradecanyl acrylate, tricyclo[8.2.1.1]tetradecanyl methacrylate, tricyclo[7.3.1.1]tetradecanyl acrylate, .Tricyclo[7.3.1.1]tetradecanyl methacrylate, tricyclo[7.2.2.1]tetradecanyl acrylate, tricyclo[7.2.2.1]tetradecanyl methacrylate, tricyclo[6.4.1.1]tetradecanyl acrylate, tricyclo[6.4.1.1]tetradecanyl methacrylate, tricyclo[6.3.2.1]tetradecanyl acrylate, tricyclo[6.3.2.1]tetradecanyl methacrylate, tricyclo[6.2.2.2]tetradecanyl acrylate, tricyclo[6.2.2.2]tetradecanyl methacrylate, tricyclo[5.5.1.1]tetradecanyl acrylate, tricyclo[5.5.1.1]tetradecanyl methacrylate, tricyclo [5.4.2.1] Tetradecanyl acrylate, tricyclo[5.4.2.1] Tetradecanyl methacrylate, tricyclo[5.3.3.1] Tetradecanyl acrylate, tricyclo[5.3.3.1] Tetradecanyl methacrylate, tricyclo[5.3.2.2] Tetradecanyl acrylate, tricyclo[5.3.2.2] Tetradecanyl methacrylate, tricyclo[4.4.2.2] Tetradecanyl acrylate, tricyclo[4.4.2.2] Tetradecanyl methacrylate, tricyclo[4.4.3.1] Tetradecanyl acrylate, tricyclo[4.4.3.2] Tetradecanyl acrylate, tricyclo[4.3.3.2] Tetradecanyl methacrylate, methyl dodecahydrofluorenyl acrylate, methyl dodecahydrofluorenyl methacrylate, dodecahydrofluorenyl methyl acrylate, dodecahydrofluorenyl methyl methacrylate, methyl dodecahydrophenalenyl acrylate, methyl dodecahydrophenalenyl methacrylate, dodecahydrophenalenyl methyl acrylate, dodecahydrophenalenyl methyl methacrylate, dodecahydroanurenyl methyl acrylate, dodecahydroanurenyl methyl methacrylate, methyl dodecahydro Nurenyl acrylate, methyl dodecahydroanurenyl methacrylate, butyl adamantyl acrylate, butyl adamantyl methacrylate, diethyl adamantyl acrylate, diethyl adamantyl methacrylate, tetramethyl adamantyl acrylate, tetramethyl adamantanyl methacrylate, ethyl dodecahydroacenaphtyrenyl acrylate, ethyl dodecahydroacenaphtyrenyl methacrylate, dimethyl dodecahydroacenaphtyrenyl acrylate, dimethyl dodecahydroacenaphtyrenyl methacrylate, ethyl dodecahydro (s) indacenyl acrylate, ethyl dodecahydro(s) indacenyl methacrylate, dimethyl dodecahydro(s) indacenyl acrylate, dimethyl dodecahydro(s) indacenyl methacrylate, ethyl dodecahydroheptarenyl acrylate, ethyl dodecahydroheptarenyl methacrylate, dimethyl dodecahydroheptarenyl acrylate, dimethyl dodecahydroheptarenyl methacrylate, bicyclo[5.4.3] tetradecanyl acrylate, bicyclo[5.4.3] tetradecanyl methacrylate, bicyclo[5.5.2] tetradecanyl methacrylate Tradecanyl acrylate, bicyclo[5.5.2]tetradecanyl methacrylate, bicyclo[6.3.3]tetradecanyl acrylate, bicyclo[6.3.3]tetradecanyl methacrylate, bicyclo[6.4.2]tetradecanyl acrylate, bicyclo[6.4.2]tetradecanyl methacrylate, bicyclo[6.5.1]tetradecanyl acrylate, bicyclo[6.5.1]tetradecanyl methacrylate, bicyclo[7.3.2]tetradecanyl acrylate, bicyclo[7.4.1] Tetradecanyl acrylate, bicyclo[7.4.1] Tetradecanyl methacrylate, bicyclo[8.2.2] Tetradecanyl acrylate, bicyclo[8.2.2] Tetradecanyl methacrylate, bicyclo[8.3.1] Tetradecanyl acrylate, bicyclo[8.3.1] Tetradecanyl methacrylate, bicyclo[9.2.1] Tetradecanyl acrylate, bicyclo[9.2.1] Tetradecanyl methacrylate, Butyl decahydronaphthalenyl acrylate, Butyl Decahydronaphthalenyl methacrylate, diethyl decahydronaphthalenyl acrylate, diethyl decahydronaphthalenyl methacrylate, tetramethyl decahydronaphthalenyl acrylate, tetramethyl decahydronaphthalenyl methacrylate, butyl decahydroazlenyl acrylate, butyl decahydroazlenyl methacrylate, diethyl decahydroazlenyl acrylate, diethyl decahydroazlenyl methacrylate, tetramethyl decahydroazlenyl acrylate, . Tetramethyldecahydroazlenyl methacrylate, pentyrooctahydroindenyl acrylate, pentyloctahydroindenyl methacrylate, hexyloctahydropentarenyl acrylate, hexyloctahydropentarenyl methacrylate, cyclohexyloctahydropentarenyl acrylate, cyclohexyloctahydropentarenyl methacrylate, hexamethylcyclooctyl acrylate, hexamethylcyclooctyl methacrylate, cyclohexylcyclooctyl acrylate, cyclohexylcyclooctyl methacrylate Lilate, heptylcycloheptyl acrylate, heptylcycloheptyl methacrylate, cycloheptylcycloheptyl acrylate, cycloheptylcycloheptyl methacrylate, cyclopentaacenaphtyrenyl acrylate, cyclopentaacenaphtyrenyl methacrylate, dicyclopentapentalenyl acrylate, dicyclopentapentalenyl methacrylate, anthracenyl acrylate, anthracenyl methacrylate, phenantrenyl acrylate, phenantrenyl methacrylate, cycloheptanaphthalenyl acrylate, Cycloheptanaphthalenyl methacrylate, bibenziyl acrylate, bibenziyl methacrylate, stilbenyl acrylate, stilbenyl methacrylate, bicycloheptatrienylidenyl acrylate, bicycloheptatrienylidenyl methacrylate, octalenyl acrylate, octalenyl methacrylate, pentadecyl acrylate, pentadecyl methacrylate, cyclopentaphenanthrene acrylate, cyclopentaphenanthrene methacrylate, hexadecyl acrylate, hexadecyl methacrylate, pyrenyl acrylate Rate, pyrenyl methacrylate, fluoranthenyl acrylate, fluoranthenyl methacrylate, aceanthrylenyl acrylate, aceanthrylenyl methacrylate, dicyclopentaheptalenyl acrylate, dicyclopentaheptalenyl methacrylate, indenoindenyl acrylate, indenoindenyl methacrylate, cyclooctaindacenyl acrylate, cyclooctaindacenyl methacrylate, cycloheptafluorenyl acrylate, cycloheptafluorenyl methacrylate,Phenylnaphthalenyl acrylate, phenylnaphthalenyl methacrylate, bicyclooctatetraenyl acrylate, bicyclooctatetraenyl methacrylate, heptadecyl acrylate, heptadecyl acrylate, methylhexadecyl acrylate, methylhexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, octadecenyl acrylate, octadecenyl methacrylate, octadecadienyl acrylate, octadecadienyl methacrylate, octadecadtrienyl acrylate, octadecadtrienyl methacrylate, cyclopentapyrenyl acrylate, cyclopentapyrenyl Nyl methacrylate, cyclopentaacetriatrilenyl acrylate, cyclopentaacetriatrilenyl methacrylate, azulenoindacenyl acrylate, azulenoindacenyl methacrylate, dicycloheptanaphthalenyl acrylate, dicycloheptanaphthalenyl methacrylate, dicyclooctapentalenyl acrylate, dicyclooctapentalenyl methacrylate, tetracenyl acrylate, tetracenyl methacrylate, tetraphenyl acrylate, tetraphenyl methacrylate, cricenyl acrylate, cricenyl methacrylate, triphenylenyl acrylate, triphenylenyl methacrylate, Cycloheptaanthracenyl acrylate, cycloheptaanthracenyl methacrylate, azurenoazlenyl acrylate, azurenoazlenyl methacrylate, nonadecyl acrylate, nonadecyl methacrylate, eicosanyl acrylate, eicosanyl methacrylate, indenofluorenyl acrylate, indenofluorenyl methacrylate, dicycloheptaindacenyl acrylate, dicycloheptaindacenyl methacrylate, perilenyl acrylate, perilenyl methacrylate, cycloheptapyrenyl acrylate, cyclohept Tapyrenyl methacrylate, dibenzofluoranteyl acrylate, dibenzofluoroanthenyl methacrylate, heptarenofluorenyl acrylate, heptarenofluorenyl methacrylate, dicycloheptanaphthalenyl acrylate, dicycloheptanaphthalenyl methacrylate, binaphthalenyl acrylate, binaphthalenyl methacrylate, viazrenyl acrylate, viazrenyl methacrylate, heneicosanyl acrylate, heneicosanyl methacrylate, azurenophenantrenyl acrylate , azulenophenantrenyl methacrylate, docosanyl acrylate, docosanyl methacrylate, pentacenyl acrylate, pentacenyl methacrylate, pentaphenyl acrylate, pentaphenyl methacrylate, picenyl acrylate, picenyl methacrylate, cycloheptazlenoheptarenyl acrylate, cycloheptazlenoheptarenyl methacrylate, tricosanyl acrylate, tricosanyl methacrylate, tetracosanyl acrylate, tetracosanyl methacrylate, coronenyl acrylate, coronenyl methacrylate Examples include, but are not limited to, tetraphenylenyl acrylate, tetraphenylenyl methacrylate, biheptalenyl acrylate, biheptalenyl methacrylate, pentacosanyl acrylate, pentacosanyl methacrylate, hexacosanyl acrylate, hexacosanyl methacrylate, hexacenyl acrylate, hexacenyl methacrylate, hexaphenyl acrylate, hexaphenyl methacrylate, bianthracenyl acrylate, bianthracenyl methacrylate, or combinations thereof.

[0026] In particular, with respect to brush copolymer compositions in accordance with this disclosure: Each R 5 Each is a linear or branched C2-C 18 The alkyl portion may also be used; each R 6 Each is a linear C8-C 20 It may be an alkyl group; each R1 and R3 may be hydrogen or methyl; each R 2 Each R may be a covalently bonded copolymer brush arm, residual hydrogen, or residual linear or branched C1-C4 hydroxyalkyl moiety; 4 Each is either linear or branched C8-C 24 It may be an alkyl group; y and z may each be 1.

[0027] In particular, with respect to brush copolymer compositions according to this disclosure, three or more of the following conditions are met (e.g., four or more, five or more, six or more, seven or more, eight or more, or all of them; in particular, five or more, seven or more, or all of them): The number average molecular weight of the brush copolymer composition, as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing about 2% (v / v) TEA as the eluent at about 40°C relative to a poly(methyl methacrylate) (PMMA) standard, is 30,000 g / mol to 100,000 g / mol; each R 5 Each is a linear or branched C2-C 18 This is the alkyl portion; each R 6 Each is a linear C8-C 20 This is the alkyl portion; each R 1 and R 3 Each R is either hydrogen or methyl; each R 4 Each is either linear or branched C8-C 24 This is the alkyl portion; y and z are each 1; each R 2 Each of these is a covalent copolymer brush arm, residual hydrogen, or residual linear or branched C1-C4 hydroxyalkyl moiety, R 2At least 70 mol% of the base is covalent 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 ratio m:n 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 skeleton; the ratio a:b 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.

[0028] In some embodiments, the copolymer skeleton can be formed by reversible deactivation radical polymerization (RDRP) methods, such as reversible addition-fragmentation-chain transfer (RAFT) polymerization. Radical initiators for such methods (one or more) include, but are not limited to, peroxides, diazo compounds, and combinations and / or hybrids thereof. In RAFT polymerization, for example, a chain transfer agent can be used simultaneously with the radical initiator(s). Suitable chain transfer agents may be selected depending on the (co)monomer system to be polymerized, for example, as described in S. Perrier, "Raft Polymerization—A User's Guide," Macromolecules, 2017, No. 50, pp. 7443-47 ("Perrier's paper"), which is incorporated herein by reference. The chain transfer agent may be selected to contain a thiocarbonylthio group, such as an aromatically substituted alkyldithionate, but is not limited to this. RAFT conditions may also be selected based on the (co)monomer system to be polymerized, as described in Perrier's paper. Such (co)polymerization may be carried out at standard pressure, reduced pressure, or high pressure. The polymerization temperature may also be varied over a wide range. In particular, polymerization may be carried out typically between approximately -20°C and approximately 200°C, for example, between approximately 50°C and approximately 150°C, or between approximately 70°C and approximately 130°C.

[0029] In some embodiments, brush copolymer compositions according to this specification, and / or individual brush arm components of brush copolymer compositions, may advantageously exhibit upper critical solution temperature (UCST) behavior at a concentration of about 5 mg / mL in a group III base stock having a kinematic viscosity (KV100) of about 4 cSt at about 100°C. To obtain such UCST behavior, turbidity analysis using ultraviolet-visible (UV-Vis) spectroscopy (e.g., by varying the temperature and monitoring a highly sensitive wavelength or wavelength group such as about 600 nm) may be utilized. In such turbidity analysis, the transition temperature (showing either dissolution or other wavelength-specific absorption / scattering) can be measured when it occurs with a transmittance of about 50%, and it is preferable to perform at least two heating and cooling cycles (within a reasonable temperature range specially selected so as not to induce significant (co)polymer degradation), and to consider only the data from heating and / or cooling cycles other than the first (e.g., to reduce, suppress, or erase previous thermal or bonding history). The UV-Vis turbidity transition of the brush arm at a wavelength of approximately 600 nm occurs in the second and subsequent cooling cycles (e.g., the second or third) at a cooling rate of approximately 1°C / min, below approximately 80.0°C (e.g., below approximately 75.0°C, below approximately 70.0°C, below approximately 65.0°C, below approximately 60.0°C, below approximately 55.0°C, below approximately 50.0°C, below approximately 45.0°C, below approximately 40.0°C, below approximately 35.0°C, or below approximately 30°C; additionally or alternatively, above approximately -40.0°C, above approximately -30.0°C, above approximately -20.0°C, above approximately -10.0°C, above approximately -0.0°C, above approximately 10.0°C, above approximately 15.0°C, or above approximately 20.0°C). (above) and / or, in the second and subsequent heating cycles (e.g., the second or third), the heating rate may be approximately 1°C / min, and the temperature may be less than approximately 85.0°C (e.g., less than approximately 80.0°C, less than approximately 75.0°C, less than approximately 70.0°C, less than approximately 65.0°C, less than approximately 60.0°C, less than approximately 55.0°C, less than approximately 50.0°C, less than 45.0°C, less than approximately 40.0°C, less than approximately 35.0°C, or less than approximately 30°C; additionally or alternatively, approximately -40.0°C or higher, approximately -30.0°C or higher, approximately -20.0°C or higher, approximately -10.0°C or higher, approximately 0.0°C or higher, approximately 10.0°C or higher, approximately 15.0°C or higher, approximately 20.0°C or higher).

[0030] Additionally or alternatively, such UCST behavior may appear in differential scanning calorimeters (DSCs) as a primary exothermic transition with a peak center at approximately 85.0°C (e.g., below approximately 80.0°C, below approximately 75.0°C, below approximately 70.0°C, below approximately 65.0°C, below approximately 60.0°C, below approximately 55.0°C, below approximately 50.0°C, below approximately 45.0°C, below approximately 40.0°C, below approximately 35.0°C, or below approximately 30°C; additionally or alternatively, above approximately -40.0°C, above approximately -30.0°C, above approximately -20.0°C, above approximately -10.0°C, above approximately 0.0°C, above approximately 10.0°C, above approximately 15.0°C, or above approximately 20.0°C) during the second and subsequent (e.g., second or third) cooling cycles at a cooling rate of approximately 1°C / min. In such DSC analysis, it is preferable to perform at least two (e.g., at least three) heating and cooling cycles (over a reasonable temperature range specially selected so as not to induce significant (co)polymer degradation), similar to the turbidity analysis described herein, and to consider only the data from heating and / or cooling cycles other than the first (e.g., to reduce, suppress, or eliminate previous thermal or bonding history). As used herein, the “primary” exothermic transition can be represented by the peak area, or alternatively by the peak height, as the largest peak (or, if multiple peaks significantly overlap, as a set of peaks).

[0031] In particular, the brush copolymer composition, the copolymer skeleton portion of the brush copolymer composition, and / or the brush arm copolymer portion of the brush copolymer composition, according to this disclosure, may have a polydispersity of less than 1.60 (for example, 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 less, or 1.20 or less) as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing about 2% (v / v) triethylamine (TEA) as the eluent at about 40°C relative to a poly(methyl methacrylate) (PMMA) standard.Additionally or alternatively, the number-average molecular weight of the brush copolymer composition, measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing approximately 2% (v / v) TEA as the eluent at approximately 40°C relative to a poly(methyl methacrylate) (PMMA) standard, ranges from 30,000 g / mol to 125,000 g / mol (e.g., 30,000 g / mol to 110,000 g / mol, 30 1,000g / mol~100,000g / mol, 30,000g / mol~90,000g / mol, 30,000g / mol~80,000g / mol, 30,000g / mol~75,000g / mol, 30,000g / mol~70,000g / mol, 30,000g / mol~65,000g / mol, 30,000g / mol~60,000g / mol, 40,000g / mol~125,000g / mol, 40,000g / mol~110 1,000g / mol, 40,000g / mol~100,000g / mol, 40,000g / mol~90,000g / mol, 40,000g / mol~80,000g / mol, 40,000g / mol~75,000g / mol, 40,000g / mol~70,000g / mol, 40,000g / mol~65,000g / mol, 45,000g / mol~125,000g / mol, 45,000g / mol~110,000g / mol, 45 ,000g / mol to 100,000g / mol, 45,000g / mol to 90,000g / mol, 45,000g / mol to 80,000g / mol, 45,000g / mol to 75,000g / mol, or 45,000g / mol to 70,000g / mol; in particular, 30,000g / mol to 100,000g / mol, 35,000g / mol to 80,000g / mol, or 40,000g / mol to 75,000g / mol).

[0032] Brush copolymers according to this disclosure may advantageously exhibit relatively high oil solubility or oil dispersibility. As used herein, the term “oil solubility” means that a composition comprising at least 0.1% by mass, preferably at least 0.5% by mass, of a comb copolymer viscosity modifier and at least 80% by mass (preferably at least 85% by mass, at least 90% by mass, or the remainder) of a lubricating oil base stock can be combined relatively easily without forming a stable macroscopic phase. Oil solubility and / or oil dispersibility may depend on the properties of the base stock, particularly the copolymer chemistry.

[0033] In some preferred embodiments, the monomers of the copolymer backbone are selected as follows. The calculated solubility parameter of the resulting copolymer backbone product (before reaction with brush arms) is a maximum of 9.46 (cal / cm³) based on the group contribution method (R. Fedors, "A Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquids," Polymer Engineering & Science, No. 14(2), February 1974, pp. 147-54). 3 ) 1 / 2 For example, up to 9.45 (cal / cm³) 3 ) 1 / 2 , maximum 9.44(cal / cm 3 ) 1 / 2 , maximum 9.43(cal / cm 3 ) 1 / 2 , maximum 9.42(cal / cm 3 ) 1 / 2 , maximum 9.41(cal / cm 3 ) 1 / 2 , maximum 9.40(cal / cm 3 ) 1 / 2 , maximum 9.38(cal / cm 3 ) 1 / 2 , maximum 9.36(cal / cm 3 ) 1 / 2 , maximum 9.34(cal / cm 3 ) 1 / 2 , 8.00~9.46, 8.00 (cal / cm 3 )1 / 2 ~9.46(cal / cm 3 ) 1 / 2 、8.00(cal / cm 3 ) 1 / 2 ~9.45(cal / cm 3 ) 1 / 2 、8.00(cal / cm 3 ) 1 / 2 ~9.44(cal / cm 3 ) 1 / 2 、8.00(cal / cm 3 ) 1 / 2 ~9.43(cal / cm 3 ) 1 / 2 、8.00(cal / cm 3 ) 1 / 2 ~9.42(cal / cm 3 ) 1 / 2 、8.00(cal / cm 3 ) 1 / 2 ~9.41(cal / cm 3 ) 1 / 2 、8.00(cal / cm 3 ) 1 / 2 ~9.40(cal / cm 3 ) 1 / 2 、8.00(cal / cm 3 ) 1 / 2 ~9.38(cal / cm 3 ) 1 / 2 、8.00(cal / cm 3 ) 1 / 2 ~9.36(cal / cm 3 ) 1 / 2 、8.00(cal / cm 3 ) 1 / 2 ~9.34(cal / cm 3 ) 1 / 2 、8.20(cal / cm 3 ) 1 / 2 ~9.46(cal / cm 3 ) 1 / 2 、8.20(cal / cm 3 ) 1 / 2 ~9.45(cal / cm 3 ) 1 / 2 、8.20(cal / cm 3 ) 1 / 2 ~9.44(cal / cm 3 ) 1 / 2 、8.20(cal / cm3 ) 1 / 2 ~9.43(cal / cm 3 ) 1 / 2 、8.20(cal / cm 3 ) 1 / 2 ~9.42(cal / cm 3 ) 1 / 2 、8.20(cal / cm 3 ) 1 / 2 ~9.41(cal / cm 3 ) 1 / 2 、8.20(cal / cm 3 ) 1 / 2 ~9.40(cal / cm 3 ) 1 / 2 、8.20(cal / cm 3 ) 1 / 2 ~9.38(cal / cm 3 ) 1 / 2 、8.20(cal / cm 3 ) 1 / 2 ~9.36(cal / cm 3 ) 1 / 2 、8.20(cal / cm 3 ) 1 / 2 ~9.34(cal / cm 3 ) 1 / 2 、8.40(cal / cm 3 ) 1 / 2 ~9.46(cal / cm 3 ) 1 / 2 、8.40(cal / cm 3 ) 1 / 2 ~9.45(cal / cm 3 ) 1 / 2 、8.40(cal / cm 3 ) 1 / 2 ~9.44(cal / cm 3 ) 1 / 2 、8.40(cal / cm 3 ) 1 / 2 ~9.43(cal / cm 3 ) 1 / 2 、8.40(cal / cm 3 ) 1 / 2 ~9.42(cal / cm 3 ) 1 / 2 、8.40(cal / cm 3 ) 1 / 2 ~9.41(cal / cm 3 ) 1 / 2、8.40(cal / cm 3 ) 1 / 2 ~9.40(cal / cm 3 ) 1 / 2 、8.40(cal / cm 3 ) 1 / 2 ~9.38(cal / cm 3 ) 1 / 2 、8.40(cal / cm 3 ) 1 / 2 ~9.36(cal / cm 3 ) 1 / 2 、8.40(cal / cm 3 ) 1 / 2 ~9.34(cal / cm 3 ) 1 / 2 、8.60(cal / cm 3 ) 1 / 2 ~9.46(cal / cm 3 ) 1 / 2 、8.60(cal / cm 3 ) 1 / 2 ~9.45(cal / cm 3 ) 1 / 2 、8.60(cal / cm 3 ) 1 / 2 ~9.44(cal / cm 3 ) 1 / 2 、8.60(cal / cm 3 ) 1 / 2 ~9.43(cal / cm 3 ) 1 / 2 、8.60(cal / cm 3 ) 1 / 2 ~9.42(cal / cm 3 ) 1 / 2 、8.60(cal / cm 3 ) 1 / 2 ~9.41(cal / cm 3 ) 1 / 2 、8.60(cal / cm 3 ) 1 / 2 ~9.40(cal / cm 3 ) 1 / 2 、8.60(cal / cm 3 ) 1 / 2 ~9.38(cal / cm 3 ) 1 / 2 、8.60(cal / cm 3 ) 1 / 2 ~9.36(cal / cm 3 )1 / 2 8.60 (cal / cm²) 3 ) 1 / 2 ~9.34 (cal / cm²) 3 ) 1 / 2 へ、8.80(cal / cm 3 ) 1 / 2 ~9.46 (cal / cm²) 3 ) 1 / 2 へ、8. 80(cal / cm 3 ) 1 / 2 ~9.45 (cal / cm²) 3 ) 1 / 2 8.80 (cal / cm²) 3 ) 1 / 2 ~9.44 (cal / cm²) 3 ) 1 / 2 8.80 (cal / cm²) 3 ) 1 / 2 ~9.43 (cal / cm²) 3 ) 1 / 2 8.80 (cal / cm²) 3 ) 1 / 2 ~9.42 (cal / cm²) 3 ) 1 / 2 8.80 (cal / cm²) 3 ) 1 / 2 ~9.41 (cal / cm²) 3 ) 1 / 2 8.80 (cal / cm²) 3 ) 1 / 2 ~9.40 (cal / cm²) 3 ) 1 / 2 8.80 (cal / cm²) 3 ) 1 / 2 ~9.38 (cal / cm²) 3 ) 1 / 2 8.80 (cal / cm²) 3 ) 1 / 2 ~9.36 (cal / cm²) 3 ) 1 / 2 8.80 (cal / cm²) 3 ) 1 / 2 ~9.34 (cal / cm²) 3 ) 1 / 2 8.90 (cal / cm²) 3 ) 1 / 2 ~9.46 (cal / cm²) 3 ) 1 / 2 8.90 (cal / cm²) 3 ) 1 / 2 ~9.45 (cal / cm²)3 ) 1 / 2 、8.90(cal / cm 3 ) 1 / 2 ~9.44(cal / cm 3 ) 1 / 2 、8.90(cal / cm 3 ) 1 / 2 ~9.43(cal / cm 3 ) 1 / 2 、8.90(cal / cm 3 ) 1 / 2 ~9.42(cal / cm 3 ) 1 / 2 、8.90(cal / cm 3 ) 1 / 2 ~9.41(cal / cm 3 ) 1 / 2 、8.90(cal / cm 3 ) 1 / 2 ~9.40(cal / cm 3 ) 1 / 2 、8.90(cal / cm 3 ) 1 / 2 ~9.38(cal / cm 3 ) 1 / 2 、8.90(cal / cm 3 ) 1 / 2 ~9.36(cal / cm 3 ) 1 / 2 、8.90(cal / cm 3 ) 1 / 2 ~9.34(cal / cm 3 ) 1 / 2 、9.00(cal / cm 3 ) 1 / 2 ~9.46(cal / cm 3 ) 1 / 2 、9.00(cal / cm 3 ) 1 / 2 ~9.45(cal / cm 3 ) 1 / 2 、9.00(cal / cm 3 ) 1 / 2 ~9.44(cal / cm 3 ) 1 / 2 、9.00(cal / cm 3 ) 1 / 2 ~9.43(cal / cm 3 ) 1 / 2 、9.00(cal / cm3 ) 1 / 2 ~9.42(cal / cm 3 ) 1 / 2 、9.00(cal / cm 3 ) 1 / 2 ~9.41(cal / cm 3 ) 1 / 2 、9.00(cal / cm 3 ) 1 / 2 ~9.40(cal / cm 3 ) 1 / 2 、9.00(cal / cm 3 ) 1 / 2 ~9.38(cal / cm 3 ) 1 / 2 、9.00(cal / cm 3 ) 1 / 2 ~9.36(cal / cm 3 ) 1 / 2 、9.00(cal / cm 3 ) 1 / 2 ~9.34(cal / cm 3 ) 1 / 2 、9.10(cal / cm 3 ) 1 / 2 ~9.46(cal / cm 3 ) 1 / 2 、9.10(cal / cm 3 ) 1 / 2 ~9.45(cal / cm 3 ) 1 / 2 、9.10(cal / cm 3 ) 1 / 2 ~9.44(cal / cm 3 ) 1 / 2 、9.10(cal / cm 3 ) 1 / 2 ~9.43(cal / cm 3 ) 1 / 2 、9.10(cal / cm 3 ) 1 / 2 ~9.42(cal / cm 3 ) 1 / 2 、9.10(cal / cm 3 ) 1 / 2 ~9.41(cal / cm 3 ) 1 / 2 、9.10(cal / cm 3 ) 1 / 2 ~9.40(cal / cm 3 ) 1 / 2, 9.10 (cal / cm 3 ) 1 / 2 ~9.38 (cal / cm 3 ) 1 / 2 , 9.10 (cal / cm 3 ) 1 / 2 ~9.36 (cal / cm 3 ) 1 / 2 , 9.10 (cal / cm 3 ) 1 / 2 ~9.34 (cal / cm 3 ) 1 / 2 , 9.20 (cal / cm 3 ) 1 / 2 ~9.46 (cal / cm 3 ) 1 / 2 , 9.20 (cal / cm 3 ) 1 / 2 ~9.45 (cal / cm 3 ) 1 / 2 9.20 (cal / cm 3 ) 1 / 2 ~9.44 (cal / cm 3 ) 1 / 2 , 9.20 (cal / cm 3 ) 1 / 2 ~9.43 (cal / cm 3 ) 1 / 2 , 9.20 (cal / cm 3 ) 1 / 2 ~9.42 (cal / cm 3 ) 1 / 2 , 9.20 (cal / cm 3 ) 1 / 2 ~9.41 (cal / cm 3 ) 1 / 2 , 9.20 (cal / cm 3 ) 1 / 2 ~9.40 (cal / cm 3 ) 1 / 2 , 9.20 (cal / cm 3 ) 1 / 2 ~9.38 (cal / cm 3 ) 1 / 2 , 9.20 (cal / cm 3 ) 1 / 2 ~9.36 (cal / cm 3 ) 1 / 2 , or 9.20 (cal / cm 3 ) 1 / 2 ~9.34 (cal / cm 3) 1 / 2 In particular, the calculated solubility parameter was a maximum of 9.46 (cal / cm³). 3 ) 1 / 2 , maximum 9.45(cal / cm 3 ) 1 / 2 , 8.20 (cal / cm 3 ) 1 / 2 ~9.46 (cal / cm 3 ) 1 / 2 , 8.60 (cal / cm 3 ) 1 / 2 ~9.45 (cal / cm 3 ) 1 / 2 , or 8.80 (cal / cm³) 3 ) 1 / 2 ~9.44 (cal / cm 3 ) 1 / 2 It is possible to do so. In Fedors' paper, the solubility parameter δ is estimated by the following calculation: δ = [(Σ i Δe i ) / (Σ i Δv i )] 1 / 2 . In the formula, Δe i Δv represents the individual energy of the i component of each repeating unit, listed in a tabulated table of vaporizations. i This represents the molar volume of the i-component of each repeating unit.

[0034] When applied to modify viscosity, brush copolymers can be combined with viscosity-modifying lubricating compositions (containing at least a lubricant base stock and optionally one or more functional lubricating composition components) to form a viscosity-modifying mixture, for example. In particular, brush copolymers may be combined with lubricating oil base stocks that optionally contain Group IV metallocene or non-metallocene base stocks and / or Group V base stocks, while also containing Group I, Group II, Group III base stocks and / or Group IV diluent / base stocks, especially at least one Group II base stock and / or at least one Group III base stock. Optionally, lubricating additives may also be included (e.g., via a small amount of lubricating oil base stock and a concentrated lubricating additive package containing one or more of the following: antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, detergents, defoamers, extreme pressure additives, pour point depressants, and seal swelling control agents; or simply via a mixture or combination of one or more of the listed additives).

[0035] For certain applications, a brush polymer (which may include additional (co)polymer components and / or additional diluents but is different from any viscosity modifier concentrate that does not contain other lubricant-based functional components) is in an amount of 0.2% to 15% by mass, such as 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, 0.2% to 2.0% 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 mass%, 1.0 mass% to 6.0 mass%, 1.0 mass% to 5.0 mass%, 1.0 mass% to 4.0 mass%, 1.0 mass% to 3.5 mass%, 1.0 mass% to 3.0 mass%, 1. 0 mass% to 2.5 mass%, 1.0 mass% to 2.0 mass%, 1.2 mass% to 15 mass%, 1.2 mass% to 12 mass%, 1.2 mass% to 9.0 mass%, 1.2 mass% to 8.0 mass% %, 1.2 mass% to 7.0 mass%, 1.2 mass% to 6.0 mass%, 1.2 mass% to 5.0 mass%, 1.2 mass% to 4.0 mass%, 1.2 mass% to 3.5 mass%, 1.2 mass% %~3.0 mass%, 1.2 mass%~2.5 mass%, 1.2 mass%~2.0 mass%, 1.4 mass%~15 mass%, 1.4 mass%~12 mass%, 1.4 mass%~9.0 mass%, 1 .4 mass% to 8.0 mass%, 1.4 mass% to 7.0 mass%, 1.4 mass% to 6.0 mass%, 1.4 mass% to 5.0 mass%, 1.4 mass% to 4.0 mass%, 1.4 mass% to 3 .5 mass%, 1.4 mass% to 3.0 mass%, 1.4 mass% to 2.5 mass%, 1.4 mass% to 2.0 mass%, 1.5 mass% to 15 mass%, 1.5 mass% to 12 mass%, 1.5 mass% The brush copolymer may be included in the lubricating composition in amounts of % 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 included in the lubricating composition in amounts of 0.5% to 12% by mass, or 1.0% to 9.0% by mass.

[0036] The lubricating oil base stock may be any suitable lubricating oil base stock known in the art. Both natural and synthetic lubricating oil base stocks may be suitable. Examples of natural lubricants include animal oils, vegetable oils (e.g., castor oil and lard), petroleum, mineral oil, coal or shale-derived oils, and combinations thereof. Specific examples of natural lubricants include, or are, mineral oil. Suitable mineral oils include all common mineral oil base stocks containing naphthenic or paraffinic oils in their chemical structure. Suitable oils may be refined by conventional methods using acids, alkalis, and clay or other agents such as aluminum chloride, or they may be extracted oils produced by solvent extraction using solvents such as phenol, sulfur dioxide, furfural, dichlorodiethyl ether, or combinations thereof. The oils may be subjected to hydrogenation or hydrorefining, dewaxing by cooling or catalytic dewaxing, hydrocracking, or a combination thereof. Suitable mineral oils may be produced from natural crude materials or composed of isomerized wax materials or residues from other refining methods.

[0037] Examples of synthetic lubricants include hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized, and copolymerized olefins (e.g., polybutylene, polypropylene, propylene, isobutylene copolymer, chlorinated polylactone, poly(1-hexene), poly(1-octene), poly-(1-decene), etc., and mixtures thereof); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, etc.); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyl, etc.); alkylated diphenyl ethers, alkylated diphenyl sulfides, and derivatives, analogs, homologs, etc. thereof; and combinations and / or reaction products thereof. In some embodiments, the synthetic oil-derived oils of this class may include or be polyalphaolefins (PAOs) containing hydrogenated oligomers of α-olefins, particularly 1-decene oligomers, for example, oligomers produced by the free radical method, Ziegler catalytic reaction, or cationic method. These may be, for example, branched or linear α-olefin oligomers having 2 to 16 carbon atoms, and specific non-limiting examples include polypropene, polyisobutene, poly-1-butene, poly-1-hexene, poly-1-octene, poly-1-decene, poly-1-dodecene, and mixtures and / or copolymers thereof.

[0038] Additionally or alternatively, synthetic lubricants include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof, in which any (most) terminal hydroxyl groups are modified by esterification, etherification, etc. Examples of synthetic oils in this class include: polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether with an average Mn of about 1000 daltons, diphenyl ethers of polypropylene glycol with an average Mn of about 1000 to about 1500 daltons); and mono- and poly-carboxylic acid esters thereof (e.g., tetraethylene glycol acetate(single or multiple), mixed C3-C8 fatty acid esters, 12 Examples include oxo acid diesters (single or multiple), or combinations thereof.

[0039] Another preferred class of synthetic lubricants may include esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) with various alcohols (e.g., 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 azelaate, diisodecyl azelaate, dioctyl phthalate, didecyl phthalate, diecosyl sebacate, 2-ethylhexyl diester of linoleate dimer, composite 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 oil types derived from synthetic oils in this class include C4-C 12 One example is alcohol adipine salts. Additionally or alternatively, esters useful as synthetic lubricants include C5-C 12 Examples include monocarboxylic acids, polyols, and / or polyol ethers, such as neopentyl glycol, trimethylolpropanepentaerythritol, dipentaerythritol, tripentaerythritol, and esters formed from combinations thereof.

[0040] Lubricating oils may be derived from unrefined oils, refined oils, re-refined oils, or mixtures thereof. Unrefined oils are obtained directly from natural or synthetic sources (e.g., coal, shale, or tar sands bitumin) without further refinement or processing. Examples of unrefined oils include shale oil obtained directly from retort processing, petroleum obtained directly from distillation, or ester oils obtained directly from esterification, each or a combination thereof may be used without further processing. Refined oils are similar to unrefined oils, with the exception that refined oils are usually processed in one or more refining steps to alter their chemical structure and / or improve one or more properties. Suitable refining techniques include distillation, hydrotreatment, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art. Re-refined oils may be obtained by processing used oil and / or refined oil in the same manner as that used to obtain the first refined oil. Such re-refined oils are known as recycled oils or reprocessed oils, and are often further treated with techniques to remove spent additives and oil hydrolysates.

[0041] Another additional or alternative class of suitable lubricants may include lubricant base stocks produced from the oligomerization of natural gas feedstocks or the isomerization of waxes. These base stocks are found in several forms, but are generally known as gas-to-liquid (GTL) or Fischer-Tropsch base stocks. Lubricant base stocks in accordance with this disclosure may be a blend of one or more of the oils / base stocks described herein, in which the oils / base stocks may be of similar or different types. Blends of natural and synthetic lubricants (i.e., partial synthesis) are expressly intended in this disclosure.

[0042] Lubricants can be classified as defined in the "Engine Oil Licensing and Certification System," published by the American Petroleum Institute (API), Industry Services Department, December 1996, 14th edition, Supplement 1, December 1998. Here, lubricants are classified as follows: a) Group I base stocks contain less than 90% saturated material and / or more than 0.03% sulfur, and have a viscosity index of 80 or more and less than 120; b) The Group II base stock contains 90% or more saturated material and 0.03% or less sulfur, and has a viscosity index of 80 or more and less than 120; c) The base stock of Group III contains 90% or more saturated material and 0.03% or less sulfur, and has a viscosity index of 120 or higher; d) The Group IV base stock is polyalphaolefin (PAO); e) Group V base stocks are all other base stock oils not included in Groups I, II, III, or IV.

[0043] In particular, the lubricating oil may contain or be composed of mineral oil or a mixture of mineral oils, especially mineral oils of Group I, Group II, Group III, and / or Group IV (of the API classification). For example, the lubricating oil base stock (including, for example, Group I, Group II, Group III, and / or Group IV) may be 55% to 98% by mass of the total mass of the lubricant composition (including the lubricating oil base stock components and any lubricating additives, and 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 8% by mass 5% by mass, 65% by mass - 98% by mass, 65% by mass - 95% by mass, 65% by mass - 90% by mass, 65% by mass - 85% by mass, 70% by mass - 98% by mass, 70% by mass - 95% by mass, 70% by mass - 90% by mass, 70% by mass - 85% by mass, 75 It may constitute % by mass 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.

[0044] Lubricating additives may contain one or more additive components, or may be contained in a (concentrated) lubricating additive package. A (concentrated) additive package typically contains a small amount of lubricating oil base stock, etc., to make the additive compatible with the remainder of the lubricant composition. However, as used herein, the term "additive" refers only to the lubricating additive in the lubricant composition, while the term "lubricating oil base stock" refers to the entire base stock, including both the base stock in the additive package and the base stock as the lubricating component that constitutes the majority phase. Additionally or alternatively, two or more additives may be added together as an additive package, or one or more other components may be added separately to the lubricating oil base stock and / or to the admixture for forming the lubricating composition. In particular, the lubricating additive may contain, or be composed of, one or more of the following: antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, cleaning agents, defoamers, extreme pressure additives, pour point depressants, optionally dyes and / or dye stabilizers, and seal swelling control agents. As the name suggests, anti-wear additives may be used to reduce wear on lubricating components, such as the crankcase and / or motor-driven parts such as the transmission. Some anti-wear components provide not only anti-wear functionality but also alternative antioxidant properties.

[0045] It is known in the art that phosphorus-containing compounds can provide wear protection to high-load contact metal surfaces. Without being bound by theory, this is suggested to be a result of the formation of a phosphorous acid "glass" on the lubricated metal surface. The phosphorus-containing anti-wear component may contain one or more, particularly two or more, or three or more, compounds of the following structure (I): [ka] (I); In the formula, groups R1, R2, and R3 each independently contain, or may contain, an alkyl group having 1 to 18 carbon atoms and / or an alkyl chain having 1 to 18 carbon atoms interrupted by a thioether bond. However, at least a portion of groups R1, R2, and R3 contains, or may contain, an alkyl group having 1 to 18 carbon atoms interrupted by a thioether bond. The mixture may contain three or more, four or more, or five or more compounds of structure (I).

[0046] In some embodiments, groups R1, R2, and R3 each independently contain, or may contain, 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 interrupted by a thioether bond. However, at least a portion of groups R1, R2, and R3 contains, or may contain, an alkyl group having 4 to 10 carbon atoms in which the alkyl chain is interrupted by a thioether bond. When groups R1, R2, and R3 contain alkyl groups (where the alkyl chain is not interrupted by a thioether bond), examples of such alkyl groups include, but are not limited to, methyl, ethyl, propyl, and butyl, particularly butyl. If groups R1, R2, and R3 include alkyl groups in which the alkyl chain is interrupted by a thioether bond, an example of such alkyl groups is the group with the structure -R'-S-R'', where R' is -(CH2) n - may be the case, n in the formula may be an integer from 2 to 4, and R'' in the formula is -(CH2) m -CH3 may also be used, and m in the formula may be an integer from 1 to 17, for example, from 3 to 9. In particular, with respect to compounds of structure (I), at least 10% by mass (e.g., at least 20% by mass, at least 30% by mass, or at least 40% by mass) of all structures (I) compounds contain a structure in which at least one of R1, R2, and R3 contains an alkyl group or is an alkyl group, wherein the alkyl group has an alkyl chain interrupted by a thioether bond and in particular has the structure -R'-S-R'', where R' is -(CH2) n It may also be -, n in the formula may be an integer from 2 to 4, R'' in the formula may be -(CH2)m-CH3, and m in the formula may be an integer from 1 to 17, for example from 3 to 9.

[0047] Another class of phosphorus-containing anti-wear additives includes one or more zinc dihydrocarbyl dithiophosphate compounds. Such compounds are well known in the art and are often called ZDDPs. These may be prepared according to known techniques, for example, by first forming dihydrocarbyl dithiophosphate (DDPA) by the reaction of one or more alcohols or phenols with P2S5, and then neutralizing the formed DDPA with a zinc compound. For example, dithiophosphate may be formed by reacting a mixture of primary and secondary alcohols. Alternatively, dithiophosphate can be prepared if the hydrocarbyl group is characteristically entirely secondary or characteristically entirely primary. Basic or neutral zinc compounds may be used to form the zinc salt, but oxides, hydroxides, and carbonates are commonly used. Commercial additives often contain excess zinc because they use an excess of basic zinc compounds in the neutralization reaction.

[0048] A favorable zinc dihydrocarbyl dithiophosphate may contain, or be a salt thereof, an oil-soluble or oil-dispersible salt of dihydrocarbyl dithiophosphate represented by the following formula: [ka] In the formula, R8 and R9 may be the same or different hydrocarbyl radicals having 1 to 18 carbon atoms (e.g., 2 to 12 or 2 to 8), and examples of such hydrocarbyl radicals include one or more alkyl, alkenyl, aryl, arylalkyl, alkalil, and alicyclic radicals. Exemplary hydrocarbyl radicals include, but are not limited to, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, amyl, 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 dispersibility, the total number of carbon atoms on each dihydrocarbyl dithiophosphate ligand (i.e., a single R8 and R9 pair) may generally be at least about 5. Therefore, in particular, zinc dihydrocarbyl dithiophosphate can contain zinc dialkyldithiophosphate or be expressed as zinc dialkyldithiophosphate.

[0049] Typically, phosphorus-free anti-wear components, which exist in a mixed form with one or more phosphorus-containing anti-wear compounds of structure (I), may contain one or more, particularly two or more, compounds of the following structure (II): [ka] In the formula, groups R4 and R7 each independently contain an alkyl group having 1 to 12 carbon atoms, or may be an alkyl group thereof, and R5 and R6 in the formula each independently contain an alkyl bond having 2 to 12 carbon atoms, or may be an alkyl bond thereof. In particular, R4 and R7 each independently contain -(CH2) m - Contains CH3 or (CH2) m -CH3 may be, where m is an integer from 1 to 17, for example from 3 to 9, and R5 and R6 are independently -(CH2) n - includes or (CH2) n- may be the case, and n in the formula is an integer between 2 and 4. The mixture may contain three or more compounds of structure (II). In particular, the mass ratio of the compound of structure (I) to the compound of structure (II) may be 2:1 to 1:2, 3:2 to 2:3, or 4:3 to 3:4. Examples of ashless dispersants include polyisobutenyl succinimide, polyisobutenyl succinamide, mixed esters / amides of polyisobutenyl-substituted succinic acid, hydroxyesters of polyisobutenyl-substituted succinic acid, as well as Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde, and polyamines, and further reaction products and mixtures thereof.

[0050] Basic nitrogen-containing ashless dispersants are well-known lubricant additives, and their preparation methods are widely reported in patent literature. Examples of dispersants include polyisobutenyl succinimide and succinamide, which have polyisobutenyl substituents with long chains of more than 36 carbon atoms, for example, more than 40. These materials can be easily formed by reacting polyisobutenyl-substituted dicarboxylic acid materials with molecules having amine functionality. Examples of suitable amines include polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Amine functionality may be imparted by polyalkylene polyamines such as tetraethylenepentamine and pentaethylenehexamine. Mixtures with an average number of nitrogen atoms per polyamine molecule exceeding 7 are also available. These polyamines are generally called heavy polyamines or H-PAMs, and some are commercially available under trade names such as HPA(trademark) and HPA-X(trademark) from Dow Chemical, and E-100(trademark) from Huntsman Chemical. Examples of hydroxysubstituted polyamines include N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, and / or N-hydroxyalkyl-alkylene polyamines such as the type of N-hydroxyalkylated alkylenediamine described in, for example, U.S. Patent No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene, polyoxypropylenediamine, and triamines with an average Mn of about 200 to about 2500 daltons. Some products of this type are marketed under the trade name Jeffamine®.

[0051] As is well known in the art, the reaction between an amine and a polyisobutenyl-substituted dicarboxylic acid material (preferably alkenyl succinic anhydride or maleic anhydride) can be conveniently achieved by heating the reactants together, for example, in an oil solution. The reaction temperature is typically about 100°C to about 250°C, and the reaction time is typically about 1 hour to about 10 hours. The reaction ratio is quite variable, but generally, the content of dicarboxylic acid units may be about 0.1 to about 1.0 equivalents per reaction equivalent of the amine-containing reactant. In particular, suitable ashless dispersants include polyisobutenyl succinic anhydride and polyisobutenyl succinimide formed from polyalkylene polyamines such as tetraethylenepentamine or H-PAM. The polyisobutenyl group may be derived from polyisobutene and may have a number-average molecular weight (Mn) of about 750 to about 5000 daltons, for example, about 900 to about 2500 daltons. As is known in the art, the dispersant may be post-treated (e.g., with a borodic / boronating agent and / or an inorganic acid of phosphorus). Suitable examples are reported in, for example, U.S. Patent No. 3,254,025, U.S. Patent No. 3,502,677, and U.S. Patent No. 4,857,214.

[0052] Detergents such as calcium-containing detergents have sufficient oil solubility or oil dispersibility to maintain dissolution or dispersion in the oil, so that they can be transported to the intended site of action by the oil. Calcium-containing detergents are known in the art and include neutral and overbasic calcium salts with acidic substances such as salicylic acid, sulfonic acid, carboxylic acid, alkylphenol, alkyl sulfide, and mixtures thereof. A neutral calcium-containing detergent is a detergent that contains an amount of calcium that is stoichiometrically equivalent to the amount of (Lewis) acidic portion present in the detergent. Therefore, neutral detergents are generally less basic than overbasic detergents.

[0053] For example, with respect to calcium detergents, the term "overbasic" is used to indicate that there is a stoichiometrically greater amount of calcium component than the corresponding (Lewis) acid component. A commonly employed method for preparing overbasic salts involves heating a mineral oil solution of the acid with a stoichiometrically excess neutralizing agent at a suitable temperature (in this case, a temperature of about 50°C, with a calcium neutralizing agent, e.g., oxides, hydroxides, carbonates, bicarbonates, sulfides, or combinations thereof), and filtering the resulting product. The use of "accelerators" in the neutralization step to promote the uptake of a significantly excess amount of salt / base (calcium in this case) is also well known. Examples of compounds useful as accelerators include, but are not limited to, phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, alkylphenol sulfide, and condensation products of formaldehyde and phenolic substances; alcohols such as methanol, 2-propanol, octanol, Cellosolve® alcohol, Carbitol® alcohol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; amines such as aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, and dodecylamine; and combinations thereof. A particularly effective method for preparing basic salts involves mixing an acidic substance with an excess amount of a calcium neutralizer and at least one alcohol accelerator, and carbonating the mixture at a high temperature, for example, 60-200°C.

[0054] Examples of useful calcium-containing cleaning agents in the lubricant compositions of this disclosure include, but are not limited to, calcium phenate; calcium phenate sulfide (e.g., each aromatic group has one or more aliphatic groups to impart hydrocarbon solubility); calcium sulfonate (e.g., each sulfonic acid moiety is bonded to an aromatic nucleus, which usually contains one or more aliphatic substituents to likewise impart hydrocarbon solubility); calcium salicylate (e.g., the aromatic moiety is usually substituted with one or more aliphatic substituents to impart hydrocarbon solubility); calcium salts of hydrolyzed phosphorusulfide olefins (e.g., 10 to 2000 carbon atoms), and / or hydrolyzed phosphorusulfide alcohols and / or aliphatic-substituted phenol compounds (e.g., 10 to 2000 carbon atoms); calcium salts of aliphatic carboxylic acids and / or aliphatic-substituted alicyclic carboxylic acids; combinations thereof and / or reaction products; and neutral and / or overbasic salts of substances such as many other similar calcium salts of oil-soluble organic acids. If necessary, a mixture of neutral and / or overbasic salts of two or more different acids can be used (for example, one or more overbasic calcium phenate and one or more overbasic calcium sulfonates).

[0055] Methods for producing oil-soluble neutral and overbasic calcium detergents are well known to those skilled in the art and are widely reported in the patent documents. Calcium-containing detergents may be optionally post-treated, for example, by boric acid treatment. Methods for preparing boric acid detergents are well known to those skilled in the art and are widely reported in the patent documents. Antioxidants, sometimes called antioxidants, can increase (or decrease) the resistance of lubricant compositions to oxidation. Antioxidants may act by binding to, modifying, and neutralizing oxidizing agents such as peroxides and other free radical-forming compounds, for example, by decomposing oxidizing agents or inactivating oxidation catalysts or accelerators. Oxidative degradation can be manifested by sludge in the fluid, varnish-like deposits on metal surfaces, and sometimes increased viscosity with increased use. Examples of suitable antioxidants include, but are not limited to, copper-containing antioxidants, sulfur-containing antioxidants, aromatic amine-containing and / or amide-containing antioxidants, hindered phenol-based antioxidants, dithiophosphates and derivatives, and combinations thereof and specific reaction products. Some antioxidants may be ashless (i.e., virtually free of metal atoms or contaminants, if present, even if in trace amounts). Corrosion inhibitors may be used to suppress metal corrosion and are often alternatively called metal deactivators or metal passivators. Some corrosion inhibitors are also characterized as antioxidants.

[0056] Suitable corrosion inhibitors include nitrogen and / or sulfur-containing heterocyclic compounds, such as triazoles (e.g., benzotriazole), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and one or more derivatives thereof. A specific corrosion inhibitor is benzotriazole represented by the following structure: [ka] In the formula, R 10 It does not exist, or C1-C 20The corrosion inhibitor is a hydrocarbyl or substituted hydrocarbyl group, which may be linear or branched, saturated or unsaturated. The corrosion inhibitor may be naturally alkyl or aromatic, and / or have a ring structure containing heteroatoms such as N, O, or S. Examples of suitable compounds include benzotriazoles, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, alkalil-substituted or aralkyl-substituted benzotriazoles, etc., and combinations thereof. For example, the triazole may include or contain benzotriazoles and / or alkylbenzotriazoles with 1 to about 20 or 1 to about 8 carbon atoms in the alkyl group. Preferred corrosion inhibitors may include or contain benzotriazoles and / or tolyltriazoles.

[0057] Additionally or alternatively, the corrosion inhibitor may include a substituted thiadiazole represented by the following structure: [ka] In the formula, R 11 and R 12 Each of these groups is independently a hydrogen or hydrocarbon group, which may be aliphatic or aromatic, such as cyclic, alicyclic, aralkyl, aryl, and alkaryl. These substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been reported in the art, and any of these compounds may be added to 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-(hydrocarbon dithio)-1,3,4-thiadiazoles.

[0058] Furthermore, the corrosion inhibitor may additionally or alternatively include one or more other derivatives of DMTD, such as carboxylic acid esters, among which R 9and R 10 The sulfur atom of the sulfide may be bonded via a carbonyl group. The preparation of these thioester-containing DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. For example, U.S. Patent No. 2,836,564 describes a DMTD derivative produced by the condensation of DMTD with an α-halogenated aliphatic monocarbonic acid having at least 10 carbon atoms. By this method, R 11 and R 12 hooc-CH(R 13 )-(R 13 DMTD derivatives are produced (where is a hydrocarbyl group). Further DMTD derivatives produced by amidation or esterification of these terminal carboxylic acid groups are also useful. The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0059] Certain classes of DMTD derivatives may include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures may be sold under the trade name HiTEC® 4313 and are commercially available from Afton Chemical. Examples of friction modifiers include derivatives of polyethylene polyamines and / or ethoxylated long-chain amines. Derivatives of polyethylene polyamines may also include succinimides with the defined structure, or they may be simple amides. Suitable succinimides derived from polyethylene polyamines include those with the following structures: [ka] In the formula, x+y may be between 8 and 15, and z may be an integer between 0 and 5, in particular x+y may be between 11 and 15 (e.g., 13), and z may be between 1 and 3. The preparation of such friction modifiers is described, for example, in U.S. Patent No. 5,840,663.

[0060] The above succinimide may be reacted with acetic anhydride to form a friction modifier exemplified by the following structure (z=1): [ka] The preparation of this friction modifier can be found, for example, in U.S. Patent Application Publication No. 2009 / 0005277. Post-reactions with other reagents, such as boro oxidizing agents, are also known in the art.

[0061] An example of an alternative simple amide may have the following structure: [ka] In the formula, R 14 and R 15 These alkyl groups may be the same or different. For example, R 14 and R 15 C is either linear or branched. 14 -C 20 It may be an alkyl group, and m can be an integer from 1 to 5. In particular, R 14 and R 15 Both can be derived from isostearic acid, and m may be 4.

[0062] Suitable ethoxylated amine friction modifiers include, or may be, reaction products of primary amines and / or diamines with ethylene oxide. The reaction with ethylene oxide may preferably be carried out stoichiometrically, such that almost all primary and secondary amines can be converted to tertiary amines. Such amines may have the following exemplary structures: [ka] In the formula, R16 and R 17 This may be an alkyl group having approximately 10 to 20 carbon atoms, or an alkyl group containing a sulfur or oxygen bond. An example of an ethoxylated amine friction modifier is R 16 and / or R 17 The material may also contain 16 to 20 carbon atoms, for example, 16 to 18. This type of material may be commercially available and is sold under the trade names Ethomeen® and Ethoduomeen® by Akzo Nobel. Preferred materials from Akzo Nobel include Ethomeen® T / 12 and Ethoduomeen® T / 13.

[0063] Another alternative type of friction modifier is oil-soluble or oil-dispersible molybdenum-containing compounds, such as oil-soluble or oil-dispersible organic molybdenum compounds. Non-limiting examples of such oil-soluble or oil-dispersible organic molybdenum compounds include, but are not limited to, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum dithiophosphinate, molybdenum xanthogenic acid, molybdenum thiooxantogenic acid, molybdenum sulfide, and mixtures thereof, particularly molybdenum dialkyldithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum alkylxanthogenic acid, and molybdenum alkylthiooxantogenic acid. Typical alkylxanthogenic acid molybdenum compounds and alkylthiooxantogenic acid molybdenum compounds are, respectively, Mo(R 18 OCS2)4 and Mo(R) 18 It may also be expressed using the formula SCS2)4. Each R in the formula 18 This may be an organic group independently selected from alkyl, aryl, aralkyl, and alkoxyalkyl groups, generally having 1 to 30 or 2 to 12 carbon atoms, particularly an alkyl group having 2 to 12 carbon atoms.

[0064] In certain embodiments, the oil-soluble or oil-dispersible organic molybdenum compound may include molybdenum dithiocarbamate, such as molybdenum dialkyldithiocarbamate, and / or may substantially not include molybdenum dithiophosphate, particularly molybdenum dialkyldithiophosphate. In certain other embodiments, any oil-soluble or oil-dispersible molybdenum compound may be composed of molybdenum dithiocarbamate, such as molybdenum dialkyldithiocarbamate, and / or molybdenum dithiophosphate, such as molybdenum dialkyldithiophosphate, as the sole source(s) of molybdenum atoms in the lubricant composition. In any combination of embodiments, the oil-soluble or oil-dispersible molybdenum compound may be substantially composed of molybdenum dithiocarbamate, such as molybdenum dialkyldithiocarbamate, as the sole source of molybdenum atoms in the lubricant composition. The molybdenum compound may be mononuclear, binuclear, trinuclear, or tetranuclear, particularly including or being binuclear and / or trinuclear molybdenum compounds.

[0065] Suitable binuclear or dimeric molybdenum dialkyldithiocarbamate can be represented, for example, by the following formula:

Chemical formula

[0066] Suitable trinuclear organic molybdenum compounds include the formula: Mo3S k L n Q zCompounds having the same, and mixtures thereof, are examples. In such a trinuclear formula, the three molybdenum atoms may be bonded to multiple sulfur atoms (S), and k is variable from 4 to 7. Furthermore, each L may be an independently selected organic ligand having a sufficient number of carbon atoms to convert the compound to oil-soluble or oil-dispersible, and n is from 1 to 4. In addition, if z is not zero, Q may be selected from the group of neutral electron-donating compounds such as water, amines, alcohols, phosphines, and / or ethers, and z is in the range of 0 to 5, including non-stoichiometric (non-integer) values. In such a trinuclear formula, all ligands (L) n In the combinations of ), there may typically be at least 21 carbon atoms in total (e.g., at least 25, at least 30, or at least 35), but the organic groups of these ligands may also have a sufficient number of carbon atoms to collectively convert the compound to oil-soluble or oil-dispersible. For example, the number of carbon atoms in each ligand L may generally be in the range of 1 to 100, for example, 1 to 30 or 4 to 20.

[0067] Formula Mo3S k L n Q z Trinuclear molybdenum compounds having this characteristic may also advantageously exhibit a cationic core surrounded by anionic ligands, as represented in one or both of the following structures: [ka] Each of these cationic cores may have a net charge of +4 (for example, due to the oxidation state of each Mo atom being +4). Therefore, in order to solubilize these cores, the total charge of all ligands must match, which in this case is -4. Four monoanionic ligands may provide an advantage in neutralizing the cores. Without intending to be bound by any theory, it is conceivable that two or more trinuclear cores may be bound or interconnected by one or more ligands, and that the ligands may be polydentate. This includes the case of polydentate ligands having multiple bonds to a single core. Oxygen and / or selenium may be substituted for some of the sulfur atoms of any of the cores.

[0068] Non-limiting examples of ligands for the trinuclear core described above include, but are not limited to, dithiophosphates such as dialkyldithiophosphates, xanthogenic acids such as alkylxanthogenic acids and / or alkylthiooxanthogenic acids, dithiocarbamates such as dialkyldithiocarbamates, and combinations thereof, in particular each containing or being a dialkyldithiocarbamate. Additionally or alternatively, the ligands for the trinuclear molybdenum-containing core may each be independently one or more of the following formulas: [ka] In the formula, X5, X6, X7, and Y are each independently oxygen or sulfur, Z is nitrogen or boron, and R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , and R 31Each of these is independently a hydrogen atom or an organic (carbon-containing) moiety such as a hydrocarbyl group, which may be the same as or different from each other, and may be particularly the same. Exemplary organic moieties include alkyl (e.g., the carbon atoms bonded to the rest of the ligand are primary or secondary), aryl, substituted aryl, alkaryl, substituted alkaryl, aralkyl, substituted aralkyl, ether, thioether, or combinations or reaction products thereof, particularly alkyl, or may be thereof.

[0069] Oil-soluble or oil-dispersible trinuclear molybdenum compounds include (NH4)2Mo3S 13 ● This can be prepared by reacting a molybdenum source such as n(H2O) (where n is variable in the range of 0 to 2, including non-stoichiometric (non-integer) values) with a suitable ligand source such as tetraalkylthiuram disulfide in a suitable liquid / solvent. Other oil-soluble or oil-dispersible trinuclear molybdenum compounds can be prepared by reacting (NH4)2Mo3S in a suitable solvent. 13 ● These compounds can be formed during the reaction of a molybdenum source such as n(H2O) with a ligand source such as tetraalkylthiuram disulfide, dialkyl dithiocarbamate, or dialkyl dithiophosphate, and a sulfur extractant such as cyanide ions, sulfite ions, or substituted phosphines. Alternatively, a trinuclear molybdenum-sulfur halide salt such as [M']2[Mo3S7A6] (wherein M' is a counterion and A is a halogen such as Cl, Br, or I) may be reacted in a suitable liquid / solvent(s) with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate to form an oil-soluble or oil-dispersible trinuclear molybdenum compound. The suitable liquid / solvent(s) may be, for example, aqueous or organic.

[0070] Other molybdenum precursors include acidic molybdenum compounds. Such compounds may react with basic nitrogen compounds when measured using the American Society for Testing and Materials (ASTM) D-664 or D-2896 titration procedure, and may typically be hexavalent. Examples include, but are not limited to, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, as well as other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds, or combinations thereof. Accordingly, additionally or alternatively, the compositions of the present disclosure may provide molybdenum by molybdenum / sulfur complexes of basic nitrogen compounds as described in, for example, 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 WO94 / 06897. Other additives known in the art, such as defoaming agents, seal swelling control agents, extreme pressure additives, pour point depressants, other viscosity modifiers, and optionally dyes and dye stabilizers, may be optionally added to the lubricant composition. These are typically disclosed, for example, in "Lubricant Additives" by CVSmallheer and R. Kennedy Smith, 1967, pp. 1-11.

[0071] Further Embodiments Additionally or alternatively, this disclosure may include one or more of the following embodiments:

[0072] Embodiment 1 A brush copolymer composition comprising a copolymer skeleton and copolymer brush arms: The copolymer brush arm comprises at least two different monomer repeating units of acylated poly(alkyleneamine) of the following formulas (1) and (2): [ka] In the formula, each R 5 Each is a hydrogen atom, or a linear or branched C1-C molecule. 24 This is the alkyl portion; each R 6 The number of carbon atoms in each R 5 It is identical to or R 5 More, but each R 5 Unlike the others, each is linear or branched C8-C 24 It is an alkyl portion; y and z are 1 or 2, respectively; the sum of m+n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arm; The copolymer skeleton comprises monomer repeating units of at least two different acrylate monomers of the following formulas (3) and (4): [ka] In the formula, each R 1 and R 3 Each R is individually a hydrogen atom, a linear or branched C1-C4 alkyl moiety, or a mixture thereof; each R 2 Each R is individually a covalent copolymer brush arm, residual hydrogen, a residual trisubstituted silyl group whose substituents are individually linear, branched, and / or cyclic C1-C8 alkyl, aryl, alkalyl, or aralkyl 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 These are individually linear, branched, and / or cyclic C8-C 30 The alkyl, aryl, alkaryl, or aralkyl moiety; the sum of a+b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer skeleton. Brush copolymer composition.

[0073] Embodiment 2 The brush polymer composition described in Embodiment 1 exhibits upper critical solution temperature (UCST) behavior at a concentration of about 5 mg / mL in a Group III base stock having a kinematic viscosity (KV100) of about 4 cSt at about 100 °C.

[0074] Embodiment 3 The UCST behavior appears as a primary exothermic transition with a peak center below about 80.0 °C at a cooling rate of about 1 °C / min during the second or third cooling of the repeated heating and cooling cycle in a differential scanning calorimeter (DSC), for the brush polymer composition described in Embodiment 2.

[0075] Embodiment 4 The copolymer brush arms exhibit upper critical solution temperature (UCST) behavior at a concentration of about 5 mg / mL in a Group III base stock having a kinematic viscosity (KV100) of about 4 cSt at about 100 °C, for the brush polymer composition described in Embodiment 1.

[0076] Embodiment 5 The UCST behavior appears as a primary exothermic transition with a peak center below about 80.0 °C at a cooling rate of about 1 °C / min during the second or third cooling of the repeated heating and cooling cycle in a differential scanning calorimeter (DSC), for the brush polymer composition described in Embodiment 4.

[0077] Embodiment 6 The polydispersity of the brush polymer composition measured by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing about 2% triethylamine (TEA) as an eluent at about 40 °C with respect to poly(methyl methacrylate) (PMMA) standard is less than 1.60, for the brush polymer composition described in Embodiment 1.

[0078] Embodiment 7 The brush copolymer composition according to Embodiment 1, wherein the polydispersity of the copolymer skeleton, copolymer brush arms, or both is less than 1.60, as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing about 2% triethylamine (TEA) as the eluent at about 40°C relative to a poly(methyl methacrylate) (PMMA) standard.

[0079] Embodiment 8 The brush copolymer composition according to Embodiment 1, wherein the number average molecular weight of the brush copolymer composition, as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing about 2% TEA as the eluent at about 40°C relative to a poly(methyl methacrylate) (PMMA) standard, is 30,000 g / mol to 100,000 g / mol.

[0080] Embodiment 9 Each R 5 Each is a linear or branched C2-C 18 It is an alkyl or alkenyl moiety; Each R 6 Each is a linear C8-C 20 It is the alkyl part; Each R 1 and R 3 These are individually hydrogen or methyl; Each R 2 These are individually covalent copolymer brush arms, residual hydrogen, or residual linear or branched C1-C4 hydroxyalkyl moieties; Each R 4 Each is either linear or branched C8-C 24 It is the alkyl part; y and z are both 1. The brush copolymer composition according to Embodiment 1.

[0081] Embodiment 10 R 2 The brush copolymer composition according to Embodiment 1, wherein at least 50 mol% of the base is a covalent copolymer brush arm.

[0082] Embodiment 11 One or more of the following conditions: The ratio a:b is between 1:14 and 1:2; The ratio m:n is between 1:25 and 2:1. The sum of a + b is 250 or less; and The sum of m+n is 75 or less. A brush copolymer composition according to Embodiment 1 that satisfies the requirements.

[0083] Embodiment 12 A brush copolymer composition comprising a copolymer skeleton and copolymer brush arms: The copolymer brush arm exhibits upper critical solution temperature (UCST) behavior at a concentration of approximately 5 mg / mL in a group III base stock having a kinematic viscosity (KV100) of approximately 4 cSt at approximately 100°C, and comprises at least two different monomer repeating units of acylated poly(alkyleneamine) of the following formulas (1) and (2): [ka] In the formula, each R 5 Each is a hydrogen atom, or a linear or branched C1-C molecule. 24 This is the alkyl portion; each R 6 The number of carbon atoms in each R 5 It is identical to or R 5 More, but each R 5 Unlike the others, each is linear or branched C8-C 24 It is the alkyl portion; y and z are each 1 or 2; The copolymer skeleton comprises monomer repeating units of at least two different acrylate monomers of the following formulas (3) and (4): [ka] In the formula, each R 1 and R 3 Each R is individually a hydrogen atom, a linear or branched C1-C4 alkyl moiety, or a mixture thereof; each R 2Each R is a covalent copolymer brush arm, residual hydrogen, a residual trisubstituted silyl group whose substituents are each linear, branched, and / or cyclic C1-C8 alkyl, aryl, alkalyl, or aralkyl 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 Each is either linear or branched C8-C 30 The alkyl, aryl, alkalic, or aralkyl moiety, The aforementioned brush copolymer composition exhibits upper critical solution temperature (UCST) behavior at a concentration of approximately 5 mg / mL in a group III base stock having a kinematic viscosity (KV100) of approximately 4 cSt at approximately 100°C. Brush copolymer composition.

[0084] Embodiment 13 The brush copolymer composition according to Embodiment 12, wherein the UCST behavior of either or both of the copolymer brush arm and the brush copolymer composition appears in a differential scanning calorimeter (DSC) as a primary exothermic transition with a peak center below approximately 80.0°C at a cooling rate of approximately 1°C / min during the second or third cooling of an iterative heating-cooling cycle.

[0085] Embodiment 14 Five or more of the following conditions: The number-average molecular weight of the brush copolymer composition, measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing approximately 2% TEA as the eluent at approximately 40°C relative to a poly(methyl methacrylate) (PMMA) standard, is 30,000 g / mol to 100,000 g / mol. Each R 5 Each is a linear or branched C2-C 18 This is the alkyl portion; each R 6 Each is a linear C8-C 20 This is the alkyl portion; each R 1 and R 3 Each R is either hydrogen or methyl; each R 4 Each is either linear or branched C8-C24 The alkyl portion; y and z are each 1; each R 2 Each of these is a covalent copolymer brush arm, residual hydrogen, or residual linear or branched C1-C4 hydroxyalkyl moiety, R 2 At least 70 mol% of the base is covalent copolymer brush arms; The sum of m+n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arm; The ratio m:n is between 1:25 and 2:1. The sum of a + b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer skeleton; The ratio a:b is between 1:14 and 1:2; The sum of a + b is 250 or less; and The sum of m+n is 75 or less: A brush copolymer composition according to Embodiment 12 that satisfies the requirements.

[0086] Embodiment 15 A method for forming a brush copolymer composition comprising a copolymer skeleton and copolymer brush arms, comprising the following steps: A step of providing a copolymer skeleton comprising monomer repeating units of at least two different acrylate monomers of the following formulas (3) and (4): [ka] In the formula, each R 1 and R 3 Each R is individually a hydrogen atom, a linear or branched C1-C4 alkyl moiety, or a mixture thereof; each R 2 Each R is a hydrogen atom, a trisubstituted silyl group whose substituents are each linear, branched, and / or cyclic C1-C8 alkyl, aryl, alkalyl, or aralkyl moiety, a linear, cyclic, or branched C1-C7 acyl moiety, a linear or branched C1-C4 hydroxyalkyl moiety, or a monovalent counterion; each R 4 These are individually linear or branched C8-C 30 A process comprising an alkyl, aryl, alkaryl, or aralkyl moiety; A step to provide a copolymer brush arm comprising at least two different monomer repeating units of acylated poly(alkyleneamine) of the following formulas (1) and (2): [ka] In the formula, each R 5 Each is a hydrogen atom, or a linear or branched C1-C molecule. 24 It is an alkyl group; each R6 has a number of carbon atoms. 5 It is identical to or R 5 More, but each R 5 Unlike the others, each is linear or branched C8-C 24 The alkyl portion; y and z are each 1 or 2, and in this process; The copolymer brush arm is formed by a cationic ring-opening polymerization (CROP) method using heterocyclic monomers containing nitrogen and oxygen atoms, where the added chain ends are terminated with stabilized heterocyclic cations; and A process of grafting copolymer brush arms onto a copolymer skeleton; R 2 Removal of and / or formation of carboxylate anions activates the acrylate monomer repeating units of formula (3) in the copolymer skeleton; and By coupling the stabilized heterocyclic cation in the copolymer brush arm to the activated repeating unit of formula (3), the copolymer brush arm is effectively grafted onto the copolymer skeleton, thereby forming a brush copolymer composition. Process performed by A method that includes this.

[0087] Embodiment 16 The method according to Embodiment 15, wherein the copolymer skeleton is formed by a reversible deactivation radical polymerization (RDRP) method.

[0088] Embodiment 17 The method according to Embodiment 15, wherein the polydispersity of the brush copolymer composition, as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing about 2% TEA as the eluent at about 40°C relative to a poly(methyl methacrylate) (PMMA) standard, is less than 1.60.

[0089] Embodiment 18 The method according to Embodiment 15, wherein the polydispersity of the copolymer skeleton, copolymer brush arms, or both is less than 1.60, as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing about 2% TEA as the eluent at about 40°C relative to a poly(methyl methacrylate) (PMMA) standard.

[0090] Embodiment 19 The method according to Embodiment 15, wherein the number average molecular weight of the brush copolymer composition, as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing 2% TEA as the eluent at approximately 40°C relative to a poly(methyl methacrylate) (PMMA) standard, is 30,000 g / mol to 100,000 g / mol.

[0091] Embodiment 20 In the method described in Embodiment 15, Each R 5 Each is a linear or branched C2-C 18 It is the alkyl part; Each R 6 Each is a linear C8-C 20 It is the alkyl part; Each R 1 and R 3 These are individually hydrogen or methyl; Each R 2 These are individually covalent copolymer brush arms, residual hydrogen, or residual linear or branched C1-C4 hydroxyalkyl moieties; Each R 4 Each is either linear or branched C8-C 24 It is the alkyl part; y and z are both 1. The method according to Embodiment 15.

[0092] Embodiment 21 The aforementioned grafting process is R 2 The method according to Embodiment 15, wherein at least 60 mol% of the base is controlled to form a covalently bonded copolymer brush arm.

[0093] Embodiment 22 One or more of the following conditions: The sum of m+n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arm; The ratio m:n is between 1:25 and 2:1. The sum of a + b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer skeleton; The ratio a:b is between 1:14 and 1:2; The sum of a + b is less than or equal to 250; and The sum of m+n is 75 or less: The method according to Embodiment 15, which satisfies the requirements.

[0094] Embodiment 23 A lubricant composition, the following: At least 70% by mass of one or more lubricating oil base stocks; Up to 25% by mass of at least one lubricating additive, including antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, cleaning agents, defoamers, extreme pressure additives, pour point depressants, seal swelling control agents, or combinations thereof; and Brush copolymer composition according to Embodiment 1, 0.5% to 12% by mass A lubricant composition containing the following:

[0095] Embodiment 24 A lubricant composition, the following: At least 70% by mass of one or more lubricating oil base stocks; Up to 25% by mass of at least one lubricating additive, including antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, cleaning agents, defoamers, extreme pressure additives, pour point depressants, seal swelling control agents, or combinations thereof; and Brush copolymer composition according to Embodiment 12, 0.5% to 12% by mass A lubricant composition containing the following:

[0096] Embodiment 25 A lubricant composition, the following: At least 70% by mass of one or more lubricating oil base stocks; Up to 25% by mass of at least one lubricating additive, including antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, cleaning agents, defoamers, extreme pressure additives, pour point depressants, seal swelling control agents, or combinations thereof; and A brush copolymer composition formed according to the method of Embodiment 15 in an amount of 0.5% to 12% by mass, wherein the brush copolymer composition exhibits upper critical solution temperature (UCST) behavior at a concentration of about 5 mg / mL in a group III base stock having a kinematic viscosity (KV100) of about 4 cSt at about 100°C. A lubricant composition containing the following:

[0097] Embodiment 26 The lubricating composition according to Embodiment 25, wherein the UCST behavior of the brush copolymer composition appears in a differential scanning calorimeter (DSC) as a primary exothermic transition with a peak center below approximately 85.0°C at a cooling rate of approximately 1°C / min during the second or third cooling of an iterative heating-cooling cycle. Next, the present invention will be described only as a non-limiting example. [Examples]

[0098] The present invention will be described in detail below with reference to examples, but this description is not intended to impose any limitations.

[0099] material 2-ethyl-2-oxazoline (EtOx, 99+%, Acros Organics, Geel, Belgium) was dried with calcium hydride before use and distilled under a nitrogen atmosphere. Methyl tosylate (MeTos, 98%, Sigma Aldrich, St. Louis, Missouri, USA) was distilled under reduced pressure under a nitrogen atmosphere and stored. Triethylamine (TEA, ≥99%, Sigma Aldrich) was distilled under a nitrogen atmosphere and stored. The ultra-dry solvents dichloromethane (99.8%) and chlorobenzene (99.8%) from Acros Organics used were stored on a molecular sieve under an inert atmosphere. Titanium(IV) n-butoxide (99%), ethanolamine, and 3-amino-1-propanol (99%) from Acros Organics were used as obtained. Initiator V-601 from Fujifilm Wako Chemicals was used as obtained. The monomers methacrylic acid (MAA, 99%, manufactured by Sigma Aldrich), 2-ethylhexyl methacrylate (EHMA, 99%, manufactured by Acros Organics), and the transfer agent 2-cyano-2-propylbenzodithioate (CPBD, >97%, manufactured by Sigma Aldrich) were used as obtained. Sodium methoxide (NaOMe, 95%) and stearic acid (95%) from Sigma Aldrich were used as obtained. Dimethylformamide (DMF, ≥99%) is manufactured by Fisher Chemical in Pittsburgh, Pennsylvania, USA.

[0100] Other acrylate monomers and macromonomers are commercially available or can be synthesized in whole or in part. For example, 2-heptadecyl-2-oxazoline (stearyl oxazoline or SteOx) is commercially available or can be formed according to the following recipe.

[0101] Monomer Synthesis - Example 1 Approximately 1.00 equivalent of stearic acid was dissolved in approximately 30 equivalents of MeOH in a 500 mL round-bottom flask equipped with a magnetic stirrer. Then, approximately 0.007 equivalents of sulfuric acid were added, and the reaction mixture was stirred under reflux at approximately 85°C overnight (approximately 8-18 hours). After that, the temperature was lowered and reflux was maintained until it reached room temperature (approximately 20-25°C). NaHCO3 was slowly added until no gas release was observed. The solvent was removed by vacuum, and the resulting methyl stearate was used as is. Subsequently, approximately 4 equivalents of ethanolamine and approximately 0.00 equivalents of sodium methoxide were added. 3 mol% was added to a round-bottom flask, which was then placed in an oil bath and heated overnight at a maximum of approximately 120°C. After the amination was complete, the reaction mixture was cooled to approximately 90°C and distilled under reduced pressure at approximately 90–160°C. Once it reached approximately 160°C, the solution was maintained at this temperature for approximately 15 minutes, after which titanium(IV) n-butoxide (approximately 0.14 equivalents) was added. The reaction mixture was then stirred overnight under reduced pressure at approximately 160°C. The crude mixture was distilled under reduced pressure at temperatures exceeding approximately 250°C to obtain 2-oxazoline. A pale yellow solid was obtained in yield of approximately 50–65%. Exemplary data: 1 H NMR (about 300MHz, CDCl3), δ (ppm): about 0.74-0.85 (m, 3H, CH2CH3), about 1.11-1.31 (m, 28H, CH2 alkyl chain), about 1.4 8-1.60(m,2H,CCH2CH2), about 2.19(t,2H,CCH2CH2), about 3.75(t,2H,CH2CH2O), about 4.14(t,2H,NCH2CH2).

[0102] Characteristic evaluation Proton nuclear magnetic resonance ( 1 ¹H NMR spectra were recorded using Bruker Avance III HD 300MHz and HD 400MHz instruments. Deuterated chloroform (CDCl3) was used as the solvent, and the signal of residual protonated chloroform (CHCl3) at approximately 7.26 ppm was used as the reference for the chemical shift δ. Data analysis was performed using TopSpin 3.2 software.

[0103] Gel permeation chromatography (GPC) measurements were performed using two different eluents depending on the solubility of the sample. (i) Tetrahydrofuran (THF) containing approximately 2% (v / v) TEA (trimethylamine). The Agilent Technologies 1260 Infinity™ instrument was equipped with a refractometer (RI), an approximately 308 nm UV detector, an approximately 5 μm PLgel™ guard column, and an approximately 5 μm PLgel™ mixed D column (approximately 300 × approximately 7.5 mm). Unless otherwise specified, the sample was flowed at approximately 1 mL / min at approximately 40°C. For calibration, poly(methyl methacrylate) standards (Agilent Technologies PMMA calibration kit, M-M-10 and M-L-10) were used. Before injection (approximately 100 μL), the sample was filtered through a PTFE membrane with a pore size of approximately 0.2 μL. (ii) Chloroform (CHCl3) containing approximately 2% (v / v) TEA. The Agilent Technologies Infinity II™ MDS instrument was equipped with a differential refractometer (DRI), viscometer (VS), dual-angle light scattermeter (LS), and multi-wavelength UV detector. The system was equipped with a 2xPLgel™ Mixed C column (approximately 300 × approximately 7.5 mm) and a PLgel™ approximately 5 μm guard column. The sample was flowed at approximately 1 mL / min at approximately 30°C. Poly(methyl methacrylate) and polystyrene standards (Agilent Technologies EasiVials™) were used for calibration. Ethanol was added as a flow rate marker. Before injection (approximately 100 μL), the sample was filtered through a GVHP membrane with a pore size of approximately 0.22 μm. In both cases, the experimental molar mass, number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity (Mw / Mn) were determined by conventional calibration using Agilent Technologies' GPC / SEC software (plots were created using OriginPro® 2019b Academic software).

[0104] Turbidity analysis to determine the transition temperature of each sample was performed using an Agilent Technologies Cary 100 UV-Vis spectrophotometer equipped with an Agilent Technologies Cary temperature control system and an Agilent Technologies 6×6 multi-cell block Peltier. Measurements were performed using Suprasil® quartz cuvettes (100-QS, optical path ≈ 10 mm, Hellma GmbH, Jena, Germany) filled with approximately 5 mg / mL solution of each polymer in YuBase® 4 diluent / base stock (SK Corporation, South Korea). For each sample, two heating / cooling cycles were performed between approximately 15°C and 85°C with a temperature gradient of approximately 1°C / min at λ ≈ 600 nm. All data were recorded using Cary WinUV® software and refined using OriginPro® 2019b (Academic) software. The reported transition temperatures were measured / calculated at approximately 50% transmittance during the second heating cycle and / or the second cooling cycle (the first heating cycle is designed to eliminate thermal histories that tend to distort the results).

[0105] Thermogravimetric analysis (TGA) was performed using a Mettler-Toledo instrument equipped with an autosampler, under an airflow of approximately 50 mL / min, a heating rate of approximately 1 °C / min, and at temperatures ranging from approximately 25 °C to approximately 550 °C. Samples (approximately 5–20 mg each) were prepared using aluminum pans. Data were recorded using Mettler-Toledo STAR. e The analysis was performed using (Trademark) software (plots were created using OriginPro (Trademark) 2019b Academic software). Differential scanning calorimetry (DSC) analysis was used with a Mettler-Toledo DSC1® equipped with an autosampler to measure thermal transitions at a flow rate of approximately 50 mL / min and a temperature range of approximately -80°C to 150°C. The heating / cooling rate was approximately 60°C / min for the first cycle (not used in subsequent calculations) and approximately 1°C / min for the subsequent two heating / cooling cycles. Samples (approximately 5-20 mg each) were prepared using aluminum pans. Data were recorded using Mettler-Toledo STAR. eAnalysis was performed using (Trademark) software (plots were created using OriginPro(Trademark) 2019b Academic software). Reported thermal transition temperatures correspond to the peak maximum or minimum values ​​(e.g., crystallization according to the exothermic tabulation), where available. Similar to turbidity measurements, reported transition temperatures are from the third (and / or second) heating cycle and / or the third (and / or second) cooling cycle (the first heating cycle is designed to exclude thermal histories that tend to distort the results).

[0106] Brush arm copolymer synthesis - Examples 2-7 and Comparative Examples A and B In the brush arm copolymers of Examples 2-7, all copolymers utilized the same initiator (methyl tosylate, or MeTos) and monomers, 2-ethyl-2-oxazoline (EtOx) and / or 2-heptadecyl-2-oxazoline (SteOx). They were all synthesized under similar monomer:initiator ratios and other reaction conditions, the only difference being the ratio between the comonomers themselves. In these examples, desired amounts of SteOx and EtOx were transferred to microwave vials equipped with magnetic stirrs, then sealed and immersed in an oil bath at approximately 130°C. After the reaction mixture was stirred with a nitrogen stream for approximately 30 minutes, stock MeTos initiator (approximately 49 mg / mL in dry chlorobenzene) was added.

[0107] [ka] Despite the simplified graphical representation in the above formulas, all EtOx-SteOx copolymers in Examples 2-7 are considered to be essentially neither block copolymers nor "block-like," but rather nearly random copolymers or something close to it. This conclusion is supported by the experimental findings of R. Hoogenboom et al., "High-Throughput Synthesis and Screening of a Library of Random and Gradient Copoly(2-oxazoline)s," Journal of Combinatorial Chemistry, No. 8(2), pp. 145-48, which found that oxazoline monomers with short alkyl chains and those with long alkyl chains have relatively similar reactivity ratios.

[0108] With respect to the above formula, the molar ratio of total monomer to initiator in the reaction mixture was approximately 50:1. Subsequently, each reaction mixture was allowed to react for the required time under cationic ring-opening (co)polymerization (CROP) conditions to achieve a nearly complete conversion rate (at least 95%, preferably at least 99%), depending on the final copolymer composition. When MeTos is used as the initiator, the "initiator" end is considered to constitute a methyl group, and the active chain end is considered to constitute one oxazolinium species of the comonomer (balancing with a counter anion such as hydroxyl) or simply the covalently bonded oxazolinium counter anion itself (e.g., a hydroxyl group). Example data: 1 H NMR (approx. 300MHz, CDCl3), δ(ppm): approx. 0.69-0.91 (m, 6H, CH2CH2CH3, C(=O)OCH2CH3), approx. 0.91-1.32 (m, 28H, CH2 alkyl chain), approx. 1.32-1.63(m,2H,NC(=O)CH2CH2), about 2.02-2.40(m,4H,NC(=O)CH2CH2,NC(=O)CH2CH3), about 3.14-3.58(m,8H,CH2 skeleton).

[0109] In comparative examples A and B, homopolymers of approximately 100% EtOx and approximately 100% SteOx were synthesized under the same conditions as the copolymers. [Table 1] Table 1 shows that the ratio of SteOx monomer to EtOx monomer was varied, while the ratio of total monomer concentration to initiator (MeTos) concentration was kept constant at approximately 50:1. In all examples and comparative examples, 1 The monomer conversion rate determined by the 1H NMR spectrum (not shown) was >99%. The CROP reaction yielded a well-defined polymer product characterized by relatively low polydispersity (PDI). For the copolymers of Examples 2-7 and the EtOx homopolymer of Comparative Example A, GPC was performed using PMMA standard with THF (mass / 2% TEA) as the eluent, resulting in Mn ms The polydispersity index (PDI, or measured Mw / Mn) was also determined. As shown by the asterisks in Table 1, in the case of the SteOx homopolymer of Comparative Example B, since it does not dissolve in THF, PMMA was used as the standard and CHCl3 (which also contains approximately 2% v / v TEA) was used as the eluent. As can be observed from the data reported in Table 1, regardless of the eluent used, in all examples and comparative examples, the measured / experimental Mn (Mn ms The value is theoretical Mn(Mn th The value is lower than ). This difference was expected, in particular, because the multiple PMMA standards used for GPC calibration are thought to show differences in the hydrodynamic volume change for the (co)polymer between the eluents. However, the result of the conversion ( 1 The uniformly narrow polydispersity values ​​obtained from the 1H NMR spectrum indicate good polymerization control of the CROP reaction under reaction conditions.

[0110] The thermal properties of Examples 2-7 and Comparative Examples A-B were evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The thermal stability of all polymers in these examples and comparative examples was up to approximately 300°C. In the DSC measurements, to eliminate the thermal history of the samples, a first rapid heating / cooling cycle from approximately -80°C to approximately 150°C was performed at approximately 60°C / min, followed by two more cycles at approximately 1°C / min. Figure 1 shows, for example, the traces of the third cooling cycle for each homopolymer and copolymer. As can be observed, each of Examples 2-7 and Comparative Example B showed a primary exothermic peak within the measured temperature range (presumably indicating crystallization or some kind of α-transition), while Comparative Example A did not show a thermal transition within the measured temperature range, as expected. Since the exothermic reaction appears as a peak indicating an α-transition, it suggests crystallization during cooling (and corresponding dissolution during heating), which indicates the behavior of the upper critical solution temperature (UCST) within the measured temperature range. The absence of thermal (α) transition behavior in Comparative Example A indicates that there is virtually no change in orderliness, and in this case, it exhibits relatively uniform solubility across the measurement temperature range (or, one could simply infer relatively uniform insolubility from the DSC data, but this is not the case for EtOx homopolymers).

[0111] Examples 2 and 7 were found to exhibit high thermal transition temperatures close to those of the SteOx homopolymer (Comparative Example B) compared to other copolymers. Without being bound by theory, this can be explained by the increased overall orderliness of the two systems. On the other hand, Example 7 had the lowest amount of EtOx and was a copolymer mainly composed of SteOx. As a result, it was found that the (randomly) interposed EtOx units did not disrupt the orderliness (crystallinity) of the long alkyl side chains of the SteOx units, allowing the SteOx units to easily align into an orderly structure, thereby bringing the transition temperature closer to that of Comparative Example B. On the other hand, Example 2 had the highest amount of EtOx (compared to the examples of the other copolymer brushes); the two monomers copolymerized in nearly equimolar amounts. Again, without being bound by theory, since their comonomers are thought to have similar reactivity, it can be assumed that they can be in alternating, close proximity states in the resulting copolymer, which may result in the system exhibiting greater overall orderliness compared to other copolymers. As a result, these polymer chains pack more easily, forming an ordered structure, which in turn leads to a relatively higher exothermic temperature. Examples 3 and 4 are found to exhibit similar thermal transition temperatures, but lower than those of the SteOx homopolymer in Comparative Example B. Without being bound by theory, the non-uniform distribution of the two comonomers along the polymer may complicate the packing dynamics between polymer chains and reduce the ordered region. This aspect is further highlighted in Example 5, which exhibits the lowest thermal transition temperature among these. However, increasing the amount of SteOx and decreasing the EtOx content leads to a more ordered system, which is found to increase the thermal transition temperature, as seen in Example 6.

[0112] The solubility behavior of Examples 2-7 and Comparative Example B in diluent oil / base stock was evaluated by turbidity measurement. Each copolymer was mixed (dissolved) in Yubase® 4 (approximately 5 mg polymer / mL diluent), then subjected to two heating / cooling cycles at approximately 15°C to 85°C, and turbidity was measured at a wavelength of approximately 600 nm. Figure 2 shows, for example, the measurement curves for the second heating cycle of each sample. All copolymers of Examples 2-7 and Comparative Example B were found to exhibit UCST-type behavior (the higher the temperature, the more soluble the sample is in the diluent oil, resulting in a fairly transparent solution with a transmittance of 100% or close to it).

[0113] However, as the temperature decreased, the transmittance decreased and the polymer mixture (solution) became heterogeneous. Without being bound by theory, this heterogeneity was thought to be due to the formation of aggregates, which may be caused by the crystallization of the long alkyl chains of the SteOx repeating units. However, it is noteworthy that in all samples, the transmittance at the lowest temperature did not drop to 0%. This suggests that the (co)polymer is only slightly soluble in the oil even at low temperatures (e.g., about 15°C). As with the DSC analysis, sample mixtures / solutions with a more orderly structure overall (Examples 2, 6, and 7) were found to exhibit relatively high transition temperatures. This is because, theoretically, high temperatures inevitably destroy the crystallinity of the (co)polymer side chains compared to other less orderly bonds. As the disorder in the (co)polymer composition increases, and consequently the orderly level in the copolymer increases, the turbidity transition temperature (estimated as the temperature at about 50% transmittance) decreases, and the SteOx content tends to increase to about 90% SteOx / 10% EtOx. The turbidity curve of the copolymer in Example 5 was found to exhibit complex turbidity (possibly two transition temperatures). Without being bound by theory, the first part of this effect is due to the dynamic decrystallization of the SteOx portion of the polymer chain, which may result in a first relatively sharp phase transition. However, as the temperature is further increased, the polymer chain expands further, solubilizing low-order or low-crystalline structures. This is the basis for a second, relatively broad transition. In Examples 2-7 and Comparative Example B, Table 2 below shows the results after the second heating (TUV turb,heat ) and the second cooling (T UV turb,cool ) Turbidity transition temperature measured during the cycle (calculated with a transmittance of approximately 50%), and thermal transition temperature (T) measured during the third cooling stage in DSC analysis. DSC th,cool The results show that the data agree relatively well, suggesting a correlation between the α-transition (peak exothermic) temperature of each (co)polymer and the phase transition (UCST behavior initiation) temperature of Yubase® 4. [Table 2]

[0114] Synthesis of brush arm copolymers - Examples 8-16 and Comparative Example C 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 molar ratio of total monomer to initiator was approximately 25:1, and in Examples 10-16, the molar ratio of total monomer to initiator was approximately 50:1. In each of these examples, the desired amount of monomer(s) was transferred to a microwave vial equipped with a magnetic stirrer, then sealed and immersed in an oil bath at approximately 130°C. After the reaction mixture was stirred with a nitrogen stream for 30 minutes, the initiator solution (dried chlorobenzene containing approximately 49 mg / mL of MeTos) was added. Each reaction mixture was 1 The reaction was carried out under cationic ring-opening (co)polymerization (CROP) conditions for the required time (approximately 60 minutes) to reach the reported monomer conversion rate determined by 1H NMR. The results are shown in Table 3 below. [Table 3]

[0115] The solubility behavior of Examples 8-16 and Comparative Example C in diluent oil / base stock was evaluated by turbidity measurement, and the results are shown in Table 4 below. Each (co)polymer was mixed (dissolved) in Yubase® 4 (approximately 5 mg polymer / mL diluent), and then subjected to two heating / cooling cycles at approximately 15°C to 85°C, and turbidity was measured at a wavelength of approximately 600 nm. Similar to Examples 2-7 and Comparative Example B above, the turbidity transition temperature was estimated as the temperature at which the transmittance reached approximately 50% in both the heating and cooling cycles. The reported values ​​are for the second cycle of each type. In addition, three heating and cooling cycles were performed using DSC, and the peak exothermic temperature of the third cooling cycle is reported. [Table 4]

[0116] As the data shows, the (co)polymers of Comparative Example C and Examples 9-11 were found to be soluble in Yubase® 4 across the turbidity analysis temperature range, while Example 8 was found to be insoluble in Yubase® 4 within the same temperature range. Furthermore, only the copolymers of Examples 12-17 were found to exhibit UCST-type behavior (the higher the temperature, the more soluble the sample is in the diluent oil, resulting in a fairly clear solution with a transmittance of 100% or close to it). However, although the copolymer of Example 14 exhibited UCST-type behavior, it should be noted that this copolymer did not completely dissolve in Yubase® 4 at the upper temperature limit of the test regime (confirmed by a transmittance level below 100% in the measurement), which may lead to errors in the measured turbidity transition values ​​(indicated by an asterisk in Table 4).

[0117] Synthesis of Skeletal Copolymers - Examples 17-20 Examples 17-20 describe the synthesis of copolymers with different ratios of methacrylic acid to 2-ethylhexyl methacrylate using the reversible addition-fragmentation-chain transfer (RAFT) (co)polymerization method, which is a type of reversible inactivation radical (RDRP) method. In Example 17, methacrylic acid (approximately 0.66 mL, approximately 7.8 mmol, MAA) and 2-ethylhexyl methacrylate (approximately 7 mL, approximately 31.2 mmol, EHMA) were transferred to a round-bottom flask equipped with a magnetic stirrer and dissolved in dimethylformamide (DMF) to a final monomer concentration of approximately 5 mol / L. A DMF solution containing approximately 22.4 mg of V-601 initiator and a DMF solution containing approximately 86 mg of 2-cyano-2-propylbenzodithioate transfer agent were added to the flask. In Example 17, the molar ratio of [MAA]:[EHMA]:[CTA]:[I] was approximately 20:80:1:0.25. In Examples 18-20, the molar ratio of the transfer agent to the initiator was the same, but the molar ratios of [MAA]:[EHMA] were approximately 30:70, 40:60, and 50:50, respectively.

[0118] [ka] Despite the simplified graphical representation in the above formulas, all MAA-EHMA copolymers in Examples 17-20 are considered not to be essentially block copolymers or "block-like," but rather to be nearly random copolymers or something close to it.

[0119] Next, each reaction mixture was foamed under a nitrogen stream for approximately 30 minutes, then the flasks were capped with silicone septums and heated in an oil bath at approximately 70°C for approximately 20 hours. Each copolymer was obtained as a pink powder by precipitation in methanol. When V-601 (bis[2-cyano-2-propanoate methyl ester]-1,2-diazene) is used as the initiator and 2-cyano-2-propyl benzodithioate, the "initiator / CTA" terminus is considered to constitute the 2-cyano-2-propyl moiety (in this case, it is the same whether it is the initiator residue or the CTA residue), and the "active" chain end is considered to be reversibly capped with the benzodithioate moiety of the CTA. The conversion is 1Determined by 1H NMR. Exemplary data: 1 H NMR (about 400MHz, CDCl3), δ (ppm): about 0.72-1.15 (m, 12H, COOHCCH3, COOCH2CCH3, CHCH2CH3, CH2CH2CH3), about 1.16-1.47 (m, 8H, CHCH2CH3, CHCH 2CH2,CH2CH2CH2,CH2CH2CH3), about 1.47-1.64(m,1H,CH2CHCH2), about 1.68-2.26(m,4H,CH2CCOOH,CH2CCOOCH2),about 3.53-4.15(m,2H,OCH2CH).

[0120] Of 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 desirable solubility in dichloromethane (DCM). Since the subsequent reaction involves grafting brush arm copolymers onto the copolymer polyacrylate backbone using DCM as the diluent / solvent, only comonomer systems with an EHMA-MAA ratio of at least approximately 3:1 (approximately 75 / 25 or more) from the acrylate monomers of formulas (4) and (3) were selected and the process was further carried out. The MAA-EHMA copolymer of Example 17 was analyzed by GPC, and most of the other examples and comparative examples were similarly analyzed. At approximately 40°C relative to PMMA standard, THF (mass / 2% v / vTEA) was used as the eluent, and Mn ms And the polydispersity index (PDI, or measured Mw / Mn) was obtained. Based on this, Example 17 yielded 17500 g / mol of Mn ms and yielded a PDI of 1.18. Mn in Example 17 th It was calculated to be approximately 17800 g / mol, 1 The conversion rate of Example 17, determined by 1H NMR, was >95%.

[0121] Graft Reaction of Brush Copolymers - Examples 21-34 and Comparative Example D The brush copolymers according to Examples 21-34 and Comparative Example D were subjected to three steps: (1) CROP of one or more 2-oxazoline monomers to form brush(co)polymer arms (polyOx); (2) RAFT of (meth)acrylate monomers to form a copolymer skeleton (poly(xMA)); and (3) graft-ont reaction of pendant functional groups of (meth)acrylate monomers on the copolymer skeleton with brush(co)polymer arms to form various brush copolymer compositions. Since steps (1) and (2) are carried out separately and are independent of each other, steps (1) and (2) may be carried out in any order or simultaneously, as long as both steps (1) and (2) are carried out before step (3) (which utilizes the products of both steps (1) and (2)).

[0122] Process 1 CROP of 2-oxazoline monomer was performed in solution. The desired amount of 2-oxazoline monomer was transferred to a microwave vial equipped with a magnetic stirrer, then sealed and immersed in an oil bath at approximately 100°C. After foaming the mixture with a nitrogen stream for 30 minutes, dry dichloromethane (DCM) was added. The final monomer concentration in DCM was approximately 4 mol / L. Subsequently, MeTos stock solution was added, and the reaction mixture was maintained at approximately 100°C for approximately 35 minutes to approximately 4 hours. The conversion rate was... 1 The results were determined by 1H NMR. The molar ratio of 2-oxazoline monomer to initiator was in the range of approximately 25:1 to 100:1.

[0123] Process 2 RAFT polymerization of methacrylic acid (MAA) and 2-ethylhexyl methacrylate (EHMA) was carried out in approximately 5 M DMF solution at approximately 70°C using 2-cyano-2-propylbenzodithioate (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 changing the ratio of the two monomers. To determine the solubility of the polymer in the graft-ont reaction solvent (dichloromethane), the molar ratio of [MAA] to [EHMA] was set to 20:80 (same as Example 17). The overall ratio of [monomer] to [CPBD] to [V-601] was 100:1:0.25 (also the same as Example 17). The monomer conversion rate was 1 This was determined by 1H NMR.

[0124] Process 3 Triethylamine (TEA) was added to the dried DCM solution of poly(xMA) obtained in step 2, and this was added by syringe to a capped microwave vial containing an oligomeric oxazoline (co)polymer chain. This (co)polymer chain is assumed to be "living" and therefore to contain oxazolinium chain ends (or its non-equilibrium isomers, or its reversible end-capped form). In one example, the molar amount of poly(xMA) was calculated to be approximately 1.4 times (approximately 20 / 14 molar ratio, or approximately 40% excess) of the 2-oxazoline (co)polymer (living) chain end, based on the concentration of pendant carboxylic acid groups in the MAA monomer repeating unit. In another example (Example 32), the molar amount of poly(xMA) was calculated to be approximately 2.8 times (approximately 20 / 7 molar ratio, or approximately 180% excess) of the 2-oxazoline (co)polymer (living) chain end, based on the concentration of pendant carboxylic acid groups in the MAA monomer repeating unit. For example, a sufficient amount of TEA (e.g., approximately 3 times the molar amount) was included to assist the graft-ont reaction by promoting the deprotonation of carboxylic acid hydrogens, thereby facilitating the reaction with the oxazolinium species at the chain ends of the 2-oxazoline(co)polymer. The target concentration of the mixture in step 3 was approximately 2 mol / L. This mixture was heated at a temperature in the range of approximately 70°C to 120°C for approximately 1 hour. The resulting graft copolymer was analyzed by GPC without further purification, and in addition to molecular weight and PDI, (if necessary) inverse superimposed integral and comparison of the integrated peak areas of the unreacted brush arm and brush copolymer were used to assist in the calculation of graft efficiency, also known as brush yield (using OriginPro 2019b Academic software).

[0125] [ka] Despite the simplified schematic representation of step 3 in the above formula, all repeating units of both the brush copolymer's backbone and brush arms are considered not to be essentially block copolymers or "block-like," but rather to be almost randomly copolymerized or close to it. Furthermore, the simplified schematic representation that the ring-opened ethyl oxazoline monomer is closest to the bond site to the backbone is arbitrary; in reality, any of the repeating units may bond at any graft point from the copolymer backbone. The asterisk is used only for convenience as a substitute symbol for initiators and terminal chain ends.

[0126] [Table 5] Details of Step 1 related to Examples 21-32 are shown in Table 5 above. These all contain EtOx and SteOx comonomers. Examples 21-24 investigate the effect of CROP reaction time on monomer conversion rate and molecular weight distribution. Example 22 is considered the most balanced reaction for comparison, and therefore the remainder of the EtOx-SteOx copolymer targeted a CROP reaction time of approximately 1 hour and a conversion rate of approximately 85-90% (the only exception being Example 31, in which increasing the target degree of copolymerization to achieve the target conversion rate level required an extension of the CROP reaction time). Examples 22, 28, and 29 investigate variations in the EtOx-SteOx comonomer ratio at a nearly constant degree of polymerization, and while the number-average molecular weight of the measured brush arms showed the expected variation, the PDI of the measured brush arms showed almost no variation. Examples 22, 30, and 31 investigated the change in the degree of polymerization of EtOx-SteOx. In these examples, slight fluctuations were measured in the number-average molecular weight of the brush arm, and only very slight fluctuations were measured in the PDI of the brush arm. In Examples 22 and 30, a CROP reaction time of about 1 hour was sufficient for both polymerization degrees 25 and 50. However, at polymerization degree 100 (Example 31), it took about four times longer to achieve a similar monomer conversion rate, and it should be noted that the measured number-average molecular weight deviated significantly from the theoretical value compared to the number-average molecular weight at lower polymerization degrees.

[0127] In each of the steps 2 of Examples 21 to 32, the skeletal copolymer synthesized in Example 17 was used. Thus, the type of poly(xMA) in Examples 21 to 32 was the same, and the relative molar amount to the chain end of the oxazoline brush arm copolymer was also the same in all examples except for Example 1 (as mentioned above, in Example 32, a different relative molar amount was calculated in order to reduce the number of oxazoline brush arm graft sites by leaving more unreacted methacrylic acid pendant groups).

[0128] [Table 6]

[0129] Details of Step 3, including Examples 21-32, are shown in Table 6 above. The grafted brush copolymers exhibit a narrow molecular weight distribution, which is approximately the same as or slightly wider than that of the brush arm copolymer itself. This strongly suggests that the grafting step is a relatively fast 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 react immediately with the (living) oxazoline brush arm chain ends, resulting in a clearly defined brush copolymer. As described in the analysis of Step 1, in Examples 21-24, the CROP time of the polyOx brush arm reaction was varied, but contrary to expectations, the brush yield also appeared to be improved compared to samples with both low monomer conversion rates and high monomer conversion rates, similar to Example 22 where the conversion rate was the target value. Therefore, probably not by chance, the grafted brush copolymer of Example 22 also had the closest agreement of the measured number-mean molecular weight to the theoretical value among these four experiments. This only facilitated the selection of the conditions in Example 22 as an example and comparison for further research. Nevertheless, the relatively high brush yields among the various monomer conversion rates in these samples indicate that the graft-ont reaction works efficiently even under less-than-optimal reaction conditions. Examples 22 and 25-27 examined the variation in graft reaction temperature, and a relatively linear correlation was observed between graft temperature and brush yield, with relatively little effect on molecular weight distribution. At lower temperatures (approximately 70 / 80°C) and higher temperatures (approximately 120°C), slightly more side reactions were observed than at intermediate temperatures (approximately 100°C), suggesting that this may reduce the solubility of the resulting graft copolymer in hydrocarbon lubricants. As noted in the analysis of Step 1, Examples 22, 28, and 29 examined the variation in the EtOx-SteOx comonomer ratio at a nearly constant degree of polymerization, and in addition to the effects noted in the analysis of Step 1, they also seemed to indicate a non-linear relationship between the decrease in brush yield and the increase in SteOx content.As noted in the analysis of Step 1, Examples 22, 30, and 31 examined the change in the degree of polymerization of EtOx-SteOx at a nearly constant comonomer ratio, and in addition to the effects noted in the analysis of Step 1, they also appeared to show that the decrease in brush yield with increasing degree of polymerization was relatively linear. This finding was perhaps not surprising, considering the effect of increasing SteOx content on brush yield in Examples 22, 28, and 29. Examples 22 and 32 examined the effect of reducing the ratio of graft chains to graft point anchors (carboxylate pendant portions of methacrylic acid repeating units), and found that the measured brush yield and number-average molecular weight were slightly lower than the theoretical values. Naturally, the reactivity / functionality of the carboxylic acid portion of the MAA copolymer decreased. However, the relatively low polydispersity of the brush copolymer, as well as the polydispersity of the brush arms themselves, promotes the chemical resilience of the graft-ont reaction even under less-than-optimal reaction conditions.

[0130] [Table 7]

[0131] To elucidate thermal and solution-based transitions, GPC and 1In addition to 1H NMR analysis, the brush copolymers of Examples 21-32 were subjected to DSC and turbidimetric analysis. Similar to the above, in DSC measurements, to remove the thermal history of the sample, a first rapid heating / cooling cycle of approximately -80°C to approximately 150°C at approximately 60°C / min was used, followed by two further cycles of approximately 1°C / min. Exothermic reactions appeared as peaks in the DSC output and showed an α-transition, suggesting crystallization during cooling (and corresponding dissolution during heating), indicating the presence of an upper critical solution temperature (UCST) behavior across the measurement temperature range. The solubility behavior of Examples 21-32 in diluent oil / base stock was evaluated by turbidimetric measurement. Each brush copolymer was mixed (dissolved) in Yubase® 4 (approximately 5 mg polymer / mL diluent), followed by two heating / cooling cycles of approximately 15°C to approximately 85°C, and turbidity was measured at a wavelength of approximately 600 nm. Similarly to the above, the turbidity transition temperature was estimated as the temperature at which transmittance was approximately 50% in both the heating and cooling cycles. The reported values ​​are for the second cycle of each type. Turbidity and DSC data, including the measured transition temperatures, are shown in Table 7 above, where available.

[0132] [Table 8] Details of Step 1, including Examples 33 and 34 and Comparative Example D, are shown in Table 8 above, along with the description of CROP as used herein. All of these CROP reactions were carried out at approximately 100°C for approximately 1 hour to achieve the reported conversion rates. All measured molecular weights showed reasonable agreement with theoretical molecular weights, and all polydispersity degrees were relatively narrow / low. In Step 2 of Examples 33 and 34 and Comparative Example D, the skeletal copolymer synthesized in Example 17 was used. Thus, the poly(xMA) in Examples 33 and 34 and Comparative Example D were identical in type and molar amount relative to the oxazoline brush arm copolymer chain ends.

[0133] [Table 9] Details of Step 3, including Examples 33-34 and Comparative Example D, are shown in Table 9 above. The grafted brush copolymers exhibited a narrow molecular weight distribution, which is almost identical to that of the brush arm copolymer itself. Compared to brush copolymers containing at least EtOx:SteOx copolymer brush arms, the brush yield of these samples was relatively low, indicating solubility issues in the Step 3 solvent, which also suggests difficulty in establishing thermal and turbidity transitions. In fact, DSC experiments demonstrated that the brush copolymers of Example 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 solution temperature (UCST) behavior across the measurement temperature range.

[0134] All patents, papers, and other material disclosures described herein are incorporated herein by reference in their entirety. Descriptions of compositions comprising, consisting of, or fundamentally comprising a plurality of specific components, as presented herein and in the appended claims, should be interpreted as also encompassing compositions formed by mixing such plurality of specific components. The principles, preferred embodiments, and modes of operation of the present invention are described in the above specification. However, since the disclosed embodiments are considered illustrative rather than limiting, the invention submitted by the applicant should be interpreted as not being limited to any particular embodiment disclosed. Those skilled in the art may make modifications without departing from the spirit of the invention.

Claims

1. A brush copolymer composition comprising a copolymer skeleton and copolymer brush arms: The copolymer brush arm comprises at least two different monomer repeating units of acylated poly(alkyleneamine) of the following formulas (1) and (2): 【Chemistry 1】 In the formula, each R 5 is individually hydrogen or a linear or branched C 1 -C 24 alkyl moiety; each R 6 has the same number of carbon atoms as each R 5 or more carbon atoms than each R 5 but is different from each R 5 and is individually a linear or branched C 8 -C 24 alkyl moiety; y and z are each 1 or 2; the sum of m + n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arm; the copolymer backbone contains monomer repeating units of at least two different acrylate monomers of the following formulas (3) and (4): 【Chemistry 2】 In the formula, each R 1 and R 3 Each is a hydrogen atom, a linear or branched carbon atom. 1 -C 4 The alkyl portion, or a mixture thereof; each R 2 Each of these is a covalent copolymer brush arm, residual hydrogen, and substituents, each individually linear, branched, and / or cyclic C 1 -C 8 A residual trisubstituted silyl group which is an alkyl, aryl, alkalyl, or aralkyl moiety, and a residual linear, cyclic, or branched C 1 -C 7 Acyl portion, residual linear or branched C 1 -C 4 The hydroxyalkyl portion is a residual monovalent counterion; each R 4 These are individually linear, branched, and / or cyclic C 8 -C 30 The alkyl, aryl, alkaryl, or aralkyl moiety; the sum of a + b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer skeleton. Brush copolymer composition.

2. A brush copolymer composition comprising a copolymer skeleton and copolymer brush arms: The copolymer brush arm exhibits upper critical solution temperature (UCST) behavior at a concentration of approximately 5 mg / mL in a group III base stock having a kinematic viscosity (KV100) of approximately 4 cSt at approximately 100°C, and comprises at least two different monomer repeating units of acylated poly(alkyleneamine) of the following formulas (1) and (2): 【Transformation 3】 In the formula, each R 5 Each of these is a hydrogen atom, or a linear or branched carbon atom. 1 -C 24 It is the alkyl portion; each R 6 The number of carbon atoms in each R 5 It is the same as or each R 5 More, but each R 5 Unlike this, each individual has a linear or branched C chain. 8 -C 24 The alkyl portion is; y and z are each 1 or 2; and the copolymer skeleton comprises monomer repeating units of at least two different acrylate monomers of the following formulas (3) and (4): 【Chemistry 4】 In the formula, each R 1 and R 3 Each is a hydrogen atom, a linear or branched carbon atom. 1 -C 4 The alkyl portion, or a mixture thereof; each R 2 Each of these is a covalent copolymer brush arm, residual hydrogen, and substituents that are individually linear, branched, and / or cyclic C 1 -C 8 A residual trisubstituted silyl group which is an alkyl, aryl, alkalyl, or aralkyl moiety, and a residual linear, cyclic, or branched C 1 -C 7 Acyl portion, residual linear or branched C 1 -C 4 The hydroxyalkyl portion is a residual monovalent counterion; each R 4 Each is either linear or branched C 8 -C 30 The alkyl, aryl, alkaryl, or aralkyl moiety is present, and the brush copolymer composition also exhibits upper critical solution temperature (UCST) behavior at a concentration of about 5 mg / mL in a group III base stock having a kinematic viscosity (KV100) of about 4 cSt at about 100°C. Brush copolymer composition.

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

4. The brush copolymer composition according to any one of claims 1 to 3, wherein the brush copolymer composition, the brush copolymer arm, or both exhibit upper critical solution temperature (UCST) behavior at a concentration of about 5 mg / mL in a group III base stock having a kinematic viscosity (KV100) of about 4 cSt at about 100°C.

5. The brush copolymer composition according to claim 4, wherein the UCST behavior appears in a differential scanning calorimeter (DSC) during the second or third cooling of an iterative heating-cooling cycle as a primary exothermic transition with a peak center below approximately 80.0°C at a cooling rate of approximately 1°C / min.

6. Each R 5 Each is a linear or branched C 2 -C 18 It is the alkyl portion; each R 6 Each is a linear C 8 -C 20 It is the alkyl portion; each R 1 and R 3 Each R is either hydrogen or methyl; each R 2 These are individually covalent copolymer brush arms, residual hydrogen, or residual linear or branched carbon atoms. 1 -C 4 It is the hydroxyalkyl portion; each R 4 Each is a linear or branched C 8 -C 24 This is the alkyl portion; y and z are each 1. A brush copolymer composition according to any one of claims 1 to 5.

7. R 2 The brush copolymer composition according to any one of claims 1 to 6, wherein at least 50 mol% or at least 60 mol% of the base is a covalent copolymer brush arm.

8. The brush copolymer composition according to any one of claims 1 to 7, wherein the copolymer skeleton is formed by a reversible deactivation radical polymerization (RDRP) method such as reversible addition-fragmentation-chain transfer (RAFT) polymerization.

9. One or more of the following conditions: The ratio a:b is between 1:14 and 1:2; The ratio m:n is between 1:25 and 2:1; The sum of a + b is 250 or less; and The sum of m + n is 75 or less. The following conditions are met, and at least two different monomer repeating units of formulas (3) and (4) have a maximum of 9.45 (cal / cm³). 3 ) 1 / 2 A brush copolymer composition according to any one of claims 1 to 8, which may provide a copolymer skeleton having a calculated solubility parameter.

10. One or more of the following conditions: The sum of m + n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arm; The ratio m:n is between 1:25 and 2:1; The sum of a + b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer skeleton; The ratio a:b is between 1:14 and 1:2; The sum of a + b is 250 or less; and The sum of m + n is 75 or less: The following conditions must be met, and optionally, at least two different monomer repeating units of formulas (3) and (4) must be 8.60 (cal / cm³). 3 ) 1 / 2 ~9.45 (cal / cm 3 ) 1 / 2 A brush copolymer composition according to any one of claims 2 to 8, which provides a copolymer skeleton having a calculated solubility parameter.

11. Three or more, five or more, seven or more, or all of the following conditions: The number-average molecular weight of the brush copolymer composition, measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) containing approximately 2% (v / v) TEA as the eluent at approximately 40°C relative to a poly(methyl methacrylate) (PMMA) standard, is 30,000 g / mol to 100,000 g / mol. Each R 5 Each is a linear or branched C 2 -C 18 This is the alkyl portion; Each R 6 Each is a linear C 8 -C 20 This is the alkyl portion; Each R 1 and R 3 These are individually hydrogen or methyl; Each R 4 Each is a linear or branched C 8 -C 24 This is the alkyl portion; y and z are both 1; Each R 2 Each of these consists of a covalent copolymer brush arm, residual hydrogen, or residual linear or branched carbon. 1 -C 4 This is the hydroxyl portion, R 2 At least 70 mol% of the base is covalent copolymer brush arms; The sum of m + n is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer brush arm; The ratio m:n is between 1:25 and 2:1; The sum of a + b is 90 mol% to 100 mol% of the average degree of polymerization of the copolymer skeleton; The ratio a:b is between 1:14 and 1:2; The sum of a + b is 250 or less; and The sum of m + n is 75 or less: The following conditions are met, and at least two different monomer repeating units of formulas (3) and (4) have a value of 8.80 (cal / cm³). 3 ) 1 / 2 ~9.44 (cal / cm 3 ) 1 / 2 A brush copolymer composition according to any one of claims 2 to 8, which may provide a copolymer skeleton having the calculated solubility parameter.

12. A method for forming a brush copolymer composition according to any one of claims 1 to 8 and 10 to 11, comprising the following steps: A step of providing a copolymer skeleton comprising monomer repeating units of at least two different acrylate monomers of the following formulas (3) and (4): 【Transformation 5】 In the formula, each R1 and R3 is, respectively, hydrogen, a linear or branched C1-C4 alkyl moiety, or a mixture thereof; each R2 is, respectively, hydrogen, a trisubstituted silyl group whose substituent is, respectively, a linear, branched, and / or cyclic C1-C8 alkyl, aryl, alkalil, or aralkyl moiety, a linear, cyclic, or branched C1-C7 acyl moiety, a linear or branched C1-C4 hydroxyalkyl moiety, or a monovalent counterion; each R4 is, respectively, a linear or branched C8-C30 alkyl, aryl, alkalil, or aralkyl moiety, and at least two different monomer repeating units of formulas (3) and (4) may provide a copolymer skeleton having a calculated solubility parameter of up to 9.46 (cal / cm³) 1 / 2; A step to provide a copolymer brush arm comprising at least two different monomer repeating units of acylated poly(alkyleneamine) of the following formulas (1) and (2): 【Transformation 6】 In the formula, each R5 is individually hydrogen or a linear or branched C1-C24 alkyl moiety; each R6 has the same number of carbon atoms as each R5 or more than each R5, but is different from each R5, and is individually a linear or branched C8-C24 alkyl moiety; y and z are each 1 or 2; in this step, the copolymer brush arm is formed by a cationic ring-opening polymerization (CROP) method using a heterocyclic monomer containing nitrogen and oxygen atoms, and the addition chain end is terminated with a stabilized heterocyclic cation; and A step of grafting copolymer brush arms onto a copolymer skeleton, comprising: activating the acrylate monomer repeating units of formula (3) in the copolymer skeleton by removing R2 and / or forming carboxylate anions; and effectively grafting the copolymer brush arms onto the copolymer skeleton by coupling the stabilized heterocyclic cations in the copolymer brush arms to the activated repeating units of formula (3), thereby forming a brush copolymer composition. A method that includes this.

13. A lubricant composition comprising: at least 70% by mass of one or more lubricating oil base stocks; up to 25% by mass of at least one lubricating additive comprising antioxidants, corrosion inhibitors, anti-wear additives, friction modifiers, dispersants, cleaning agents, defoamers, extreme pressure additives, pour point depressants, seal swelling control agents, or combinations thereof; and 0.5% to 12% by mass of a brush copolymer composition according to any one or more of claims 1 to 11. A lubricant composition containing the following:

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