Polyalkyl(meth)acrylate-based polymers with improved low temperature performance

Abstract

The present invention relates to polyalkyl(meth)acrylate-based polymers containing defined amounts of long-chain alkyl(meth)acrylates, their preparation, lubricant compositions containing such polymers, and their use to improve the thickening efficiency and low temperature performance of lubricant compositions, particularly engine oil (EO) compositions.

Description

[Technical Field]

[0001] The present invention relates to polyalkyl(meth)acrylate-based polymers containing defined amounts of long-chain alkyl(meth)acrylates, their preparation, lubricant compositions containing such polymers, and their use to improve the thickening efficiency and low temperature performance of lubricant compositions, particularly engine oil (EO) compositions. [Background technology]

[0002] Polyalkyl(meth)acrylate based polymers are well known in the art to be efficient VI improvers.

[0003] U.S. Patent No. 5,565,130 discloses comb polymers and their use as viscosity index improvers. The examples contain 10-80% macromonomer and 20-90% C1-10 alkyl (meth)acrylate, exhibiting molecular weights Mw ranging from 119,000 to 325,000 g / mol. The effect of the proposed comb polymers on thickening efficiency and low-temperature performance is not disclosed therein.

[0004] WO 2007 / 003238 describes oil-soluble comb polymers based on polyolefin-based macromonomers, particularly polybutadiene-based methacrylates, and C1-C10 alkyl methacrylates. Examples contain 37.2-53.3% macromonomer, 12.3-61% C1-4 alkyl (meth)acrylate, and 12-42.6% styrene. The weight-average molecular weights Mw of the examples range from 79,000 to 402,000 g / mol, and D varies from 3.7 to 16.6.

[0005] The comb polymers can be used as additives in lubricating oils to improve viscosity index and shear stability. However, the effect of the proposed comb polymers on thickening efficiency and low temperature performance is not disclosed therein.

[0006] U.S. Patent Application Publication No. 2010 / 0190671 discloses the use of polyolefin-based macromonomers, particularly polybutadiene-based methacrylates and comb polymers based on C1-C10 alkyl methacrylates, to improve automotive fuel economy. The weight-average molecular weights Mw of the examples range from 191,000 to 374,000 g / mol, and D varies from 3.5 to 4.5. However, the effect of the proposed comb polymers on low-temperature performance is not disclosed therein.

[0007] WO 2018 / 041755 relates to selected comb polymers containing specific amounts of macromonomer and alkyl acrylate. The presence of 0.5% to 11% by weight of C4-18 alkyl acrylate positively impacts the Noack volatility of lubricating compositions containing such comb polymers. However, the effect of the proposed comb polymers on low-temperature performance is not disclosed therein.

[0008] WO 2019 / 012031 relates to comb polymers containing imide functional groups and their use to reduce wear and fuel consumption in engine oil compositions. The effect of the proposed comb polymers on low temperature performance is not disclosed therein.

[0009] EP 3839017 A1 relates to polyalkyl(alk)acrylate comb polymers containing at least 21 wt % C12-24 alkyl(alk)acrylate ester monomers. However, the effect of the proposed comb polymers on low temperature performance is not disclosed therein.

[0010] Lubricants must have a sufficiently high viscosity at operating temperatures to prevent damage to machinery or equipment. Because the viscosity of a fluid is strongly temperature dependent, a special focus is placed on ensuring minimum viscosities at maximum elevated temperatures. These viscosities are often specified, for example, as minimum kinematic viscosity at 100°C (KV100) and / or minimum high-temperature high-shear viscosity at 150°C (HTHS150).

[0011] In most cases, it is theoretically possible to adjust the lubricant viscosity at high temperatures to the required minimum by simply blending lighter and heavier base oils, but the resulting lubricant will not ensure safe and good operation of the equipment under cold start-up conditions.

[0012] Mineral oil base oils contain a certain amount of paraffinic species that tend to form wax crystals and precipitate at low temperatures. Heavier base oils contain more wax than lighter oils, and using too many waxy base oil components can result in too little low temperature fluidity.

[0013] Pour point depressants (PPDs) are used to partially mitigate the adverse effects caused by paraffin crystallization, but this alone is typically not sufficient to meet the viscosity requirements at low and high temperatures. Therefore, the viscosity of lubricants is often adjusted by the addition of viscosity index improvers (VIIs), also known as viscosity modifiers (VMs).

[0014] Lighter base oils with sufficient low-temperature fluidity are thickened with VM to the desired high-temperature value. At high temperatures, the polymer molecules uncoil, but their hydrodynamic volume increases, resulting in a greater thickening effect. At lower temperatures, the same polymer chains coil, resulting in a smaller thickening effect. This minimizes the parasitic energy losses caused by the lubricant, resulting in, for example, higher engine efficiency and lower fuel consumption.

[0015] At high temperatures, lubricants have the corresponding viscosity and form thicker oil films, providing better lubrication (=lower friction) and better wear protection. However, great care must be taken to select the appropriate VM, as it must have sufficient shear stability to withstand mechanical stress. Otherwise, it will result in undesirable viscosity loss and, again, too low a viscosity of the lubricant. The combination of light base oils, heavy base oils, one or more PPDs, and VMs, in addition to other additives, in lubricants is well known to those skilled in the art. It is also a well-known and recognized fact that as the number of additives and components increases, the cost of the resulting lubricant increases. Moreover, it is not just the cost of the individual additives that adds up, but also the complexity of the operations required to blend these lubricants, further increasing costs. Therefore, all lubricant formulators strive to maximize the use of heavier base oils while minimizing the use of other additives.

[0016] The objective of this invention was to combine the properties of a viscosity modifier with those of a pour point depressant in one molecule, while maintaining all the desirable properties of a viscosity modifier, such as VI-lift properties (both high-shear and low-shear viscosities), shear stability, and good low-temperature performance. The goal was to formulate a high-tier, multi-purpose lubricant that meets a range of demanding gear and engine oil viscosity specifications using a slate of mineral base oils and viscosity modifiers, without the need for one or more additional PPDs.

[0017] It has now surprisingly been found that polyalkyl(meth)acrylate-based polymers containing a certain amount of long-chain alkyl(meth)acrylates provide improved low temperature performance in lubricant compositions, particularly engine oil (EO) compositions. DETAILED DESCRIPTION OF THE INVENTION

[0018] A first object of the present invention is to provide a method for producing a polymerizable composition comprising the following monomers: (a) 5% to 15% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 2% by weight of methyl methacrylate; (c) 45% to 80% by weight of n-butyl methacrylate; (d) 0% to 20% by weight of a C5-11 alkyl methacrylate, preferably isodecyl methacrylate; (e) 0.2 wt% to 18 wt% of a C12-15 alkyl methacrylate, preferably a C12-14 alkyl methacrylate; (f) 2% to 19.8% by weight of a C16-20 alkyl methacrylate, preferably stearyl methacrylate, and (g) 0% to 2% by weight of styrene monomer and the total amount of component (e) and component (f) is 20% by weight or less.

[0019] The content of each of the components (a), (b), (c), (d), (e), (f) and (g) is based on the total composition of the polyalkyl(meth)acrylate polymer.

[0020] In certain embodiments, the proportions of components (a), (b), (c), (d), (e), (f) and (g) total 100% by weight.

[0021] A further object of the present invention is to provide a process for the preparation of a compound comprising the following monomers: (a) 6% to 12% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 1% by weight of methyl methacrylate; (c) 45% to 70% by weight of n-butyl methacrylate; (d) 0% by weight to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2 wt% to 18 wt% of a C12-15 alkyl methacrylate, preferably LMA; (f) 2% to 19.8% by weight of a C16-20 alkyl methacrylate, preferably SMA, and (g) 0% to 1% by weight of styrene monomer and the total amount of component (e) and component (f) is 20% by weight or less.

[0022] A further object of the present invention is to provide a process for the preparation of a compound comprising the following monomers: (a) 9% to 12% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 1% by weight of methyl methacrylate; (c) 60% to 70% by weight of n-butyl methacrylate; (d) 0% by weight to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2 wt% to 18 wt% of a C12-15 alkyl methacrylate; (f) 2% to 19.8% by weight of a C16-20 alkyl methacrylate, and (g) 0% to 1% by weight of styrene monomer and the total amount of component (e) and component (f) is 20% by weight or less.

[0023] The content of each of the components (a), (b), (c), (d), (e), and (f) is based on the total composition of the polyalkyl(meth)acrylate polymer.

[0024] In certain embodiments, the proportions of components (a), (b), (c), (d), (e), and (f) total 100% by weight.

[0025] The weight-average molecular weight of the polyalkyl(meth)acrylate polymer according to the present invention is preferably in the range of 100,000 g / mol to 1,000,000 g / mol, more preferably 300,000 g / mol to 900,000 g / mol, and particularly preferably 500,000 g / mol to 900,000 g / mol. The number-average molecular weight of the polyalkyl(meth)acrylate comb polymer according to the present invention is preferably in the range of 100,000 g / mol to 300,000 g / mol, more preferably 100,000 g / mol to 200,000 g / mol, and particularly preferably 110,000 g / mol to 160,000 g / mol.

[0026] In the context of the present invention, a polyalkyl(meth)acrylate-based polymer comprises a first polymer, also called the backbone or main chain, and a number of additional polymers, called side chains, covalently bonded to the main chain. In this case, the backbone of the polyalkyl(meth)acrylate-based polymer is formed by the crosslinked unsaturated groups of the above-mentioned (meth)acrylate. The ester groups of the (meth)acrylic acid esters, the phenyl radicals of the styrene monomers, and the substituents of the additional free-radically polymerizable comonomers form the side chains of the polyalkyl(meth)acrylate-based polymer.

[0027] The term "methacrylate" refers to an ester of methacrylic acid, and the term "(meth)acrylate" refers to both esters of acrylic acid and esters of methacrylic acid.

[0028] The hydroxylated hydrogenated polybutadienes for use according to the invention have number-average molar masses Mn of 4,000 to 6,000 g / mol, preferably 4,500 to 5,000 g / mol. Due to their high molar mass, the hydroxylated hydrogenated polybutadienes may also be referred to as macroalcohols in the context of the present invention.

[0029] The number-average molar mass Mn is determined by size exclusion chromatography using commercially available polybutadiene standards. The determination is carried out in accordance with DIN 55672-1 by gel permeation chromatography using THF as the eluent.

[0030] Preferably, the hydroxylated hydrogenated polybutadiene has a hydrogenation level of at least 99%. An alternative measure of the hydrogenation level that can be determined for the copolymer of the present invention is the iodine value. The iodine value refers to the number of grams of iodine that can be added to 100 g of copolymer. Preferably, the copolymer of the present invention has an iodine value of 5 g or less of iodine per 100 g of copolymer. The iodine value is determined by the Wijs method according to DIN 53241-1:1995-05.

[0031] A preferred hydroxylated hydrogenated polybutadiene can be obtained according to British Patent Specification No. 2270317.

[0032] Some hydroxylated hydrogenated polybutadienes are also commercially available, such as hydrogenated polybutadiene (also called olefin copolymer OCP) with OH functionalization to about 98% by weight, having about 50% 1,2 repeat units and about 50% 1,4 repeat units, respectively, and Mn=4200 g / mol, manufactured by Cray Valley (Paris), a subsidiary of Total (Paris).

[0033] Monohydroxylated hydrogenated polybutadiene is preferred. More preferably, the hydroxylated hydrogenated polybutadiene is hydroxyethyl- or hydroxypropyl-terminated hydrogenated polybutadiene. Hydroxypropyl-terminated polybutadiene is especially preferred.

[0034] These monohydroxylated hydrogenated polybutadienes can be prepared by first converting butadiene monomers to polybutadiene by anionic polymerization. Hydroxy-functionalized polybutadienes can then be prepared by reacting the polybutadiene monomers with ethylene oxide or propylene oxide. This hydroxylated polybutadiene can then be hydrogenated in the presence of a suitable transition metal catalyst.

[0035] The esters of (meth)acrylic acid and the hydroxylated hydrogenated polybutadienes described for use according to the invention are also referred to as macromonomers in the context of the present invention due to their high molar mass.

[0036] The macromonomers for use in accordance with the present invention can be prepared by transesterification of alkyl (meth)acrylates. The reaction of alkyl (meth)acrylates with hydroxylated hydrogenated polybutadiene forms the esters of the present invention. It is preferred to use methyl (meth)acrylate or ethyl (meth)acrylate as the reactant.

[0037] This transesterification reaction is widely known. For example, for this purpose, heterogeneous catalyst systems such as lithium hydroxide / calcium oxide mixtures (LiOH / CaO), pure lithium hydroxide (LiOH), lithium methoxide (LiOMe), or sodium methoxide (NaOMe) can be used, or homogeneous catalyst systems such as isopropyl titanate (Ti(OiPr)4) or dioctyltin oxide (Sn(OCt)2O). The reaction is an equilibrium reaction. Therefore, the released low molecular weight alcohol is typically removed, for example, by distillation.

[0038] Furthermore, the macromonomers can be obtained, for example, by a direct esterification step from (meth)acrylic acid or (meth)acrylic anhydride, preferably under acid catalysis with p-toluenesulfonic acid or methanesulfonic acid, or from free methacrylic acid by the DCC method (dicyclohexylcarbodiimide).

[0039] Additionally, the hydroxylated hydrogenated polybutadienes of the present invention can be converted to esters by reaction with acid chlorides such as (meth)acryloyl chloride.

[0040] Preferably, in the above detailed preparation of the esters of the invention, a polymerization inhibitor is used, such as 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl radical and / or hydroquinone monomethyl ether.

[0041] The C5-11 alkyl (meth)acrylates for use in accordance with the present invention are esters of acrylic or methacrylic acid with alcohols having 5 to 11 carbon atoms. The term "C5-11 alkyl (meth)acrylate" encompasses individual acrylic or methacrylic acid esters with alcohols of a particular length, as well as mixtures of methacrylic acid esters with alcohols of different lengths.

[0042] Suitable C5-11 alkyl (meth)acrylates include, for example, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, and undecyl (meth)acrylate.

[0043] A particularly preferred C5-11 alkyl (meth)acrylate is a methacrylic acid ester of isodecyl methacrylate.

[0044] The C12-15 alkyl (meth)acrylates for use in accordance with the present invention are esters of acrylic or methacrylic acid with alcohols having 12 to 15 carbon atoms. The term "C12-15 alkyl (meth)acrylate" encompasses individual acrylic or methacrylic acid esters with alcohols of a particular length, as well as mixtures of methacrylic acid esters with alcohols of different lengths.

[0045] Suitable C12-15 alkyl (meth)acrylates include, for example, 5-methyl-undecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl methacrylate, and pentadecyl (meth)acrylate.

[0046] Particularly preferred C11-15 alkyl (meth)acrylates are methacrylic acid esters of linear C12-14 alcohol mixtures, and most preferred are C12-14 alkyl methacrylates.

[0047] The C16-20 alkyl (meth)acrylates for use in accordance with the present invention are esters of (meth)acrylic acid and linear or branched alcohols having 16 to 20 carbon atoms. The term "C16-20 alkyl methacrylate" encompasses individual (meth)acrylic acid esters having alcohols of a particular length, as well as mixtures of (meth)acrylic acid esters having alcohols of different lengths.

[0048] Suitable C16-20 alkyl (meth)acrylates include, for example, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate.

[0049] The polyalkyl(meth)acrylate-based polymers according to the present invention can be prepared by free radical polymerization and related methods of controlled free radical polymerization, such as ATRP (atom transfer radical polymerization) or RAFT (reversible addition fragmentation chain transfer).

[0050] Standard free radical polymerization is described in detail, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition. Generally, a polymerization initiator and optionally a chain transfer agent are used for this purpose.

[0051] Initiators that can be used include azo initiators that are widely known in the art, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, as well as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5- Examples of suitable chain transfer agents include dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, bis(4-tert-butylcyclohexyl)peroxydicarbonate, mixtures of two or more of the aforementioned compounds with each other, and mixtures of the aforementioned compounds with unspecified compounds capable of forming free radicals in the same way. Suitable chain transfer agents are, in particular, oil-soluble mercaptans, such as n-dodecyl mercaptan or 2-mercaptoethanol, or chain transfer agents from the terpene class, such as terpinolene.

[0052] The ATRP process itself is known. It is hypothesized to be a "living" free radical polymerization, but no limitation by way of explanation of the mechanism is intended. In these processes, a transition metal compound is reacted with a compound having a transferable atomic group. This involves the transfer of the transferable atomic group to the transition metal compound, resulting in oxidation of the metal. This reaction forms a free radical that adds to the ethylene group. However, because the transfer of the atomic group to the transition metal compound is reversible, the atomic group can transfer back to the growing polymer chain, forming a controlled polymerization system. Therefore, it is possible to control the polymer formation, molecular weight, and molecular weight distribution.

[0053] This reaction regime is described, for example, in J.-S. Wang et al., J. Am. Chem. Soc., vol. 117, pp. 5614-5615 (1995); Matyjaszewski, Macromolecules, vol. 28, pp. 7901-7910 (1995). Furthermore, patent applications WO 96 / 30421, WO 97 / 47661, WO 97 / 18247, WO 98 / 40415 and WO 99 / 10387 disclose variants of the ATRP described above. Furthermore, the polymer of the present invention can also be obtained, for example, by the RAFT method. This method is described in detail, for example, in WO 98 / 01478 and WO 2004 / 083169.

[0054] The polymerization can be carried out under normal pressure, reduced pressure, or elevated pressure. The polymerization temperature is also not critical. However, it is generally in the range of -20°C to 200°C, preferably 50°C to 150°C, and more preferably 80°C to 130°C.

[0055] The polymerization can be carried out with or without a solvent. The term "solvent" should be understood in a broad sense here. The solvent is selected according to the polarity of the monomers used, and preferably, 100N oil, relatively light diesel oil and / or aromatic hydrocarbons, such as toluene or xylene, can be used.

[0056] The polyalkyl(meth)acrylate-based polymers according to the invention can be used in all common grades of motor oils having the viscosity characteristics defined in document SAE J300.

[0057] The second object of the present invention is to (A) 60% to 80% by weight of a base oil, and (B) a monomer of: (a) 5% to 15% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 2% by weight of methyl methacrylate; (c) 45% to 80% by weight of n-butyl methacrylate; (d) 0% by weight to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2 wt% to 18 wt% of a C12-15 alkyl methacrylate; (f) 2% to 19.8% by weight of a C16-20 alkyl methacrylate, and (g) 0% to 2% by weight of styrene monomer and 20% by weight to 40% by weight of a polyalkyl (meth)acrylate polymer, wherein the total amount of component (e) and component (f) is 20% by weight or less. The present invention relates to an additive composition comprising:

[0058] A second object of the present invention is to (A) 60% to 80% by weight of a base oil, and (B) a monomer of: (a) 6% to 12% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 1% by weight of methyl methacrylate; (c) 45% to 70% by weight of n-butyl methacrylate; (d) 0% by weight to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2 wt% to 18 wt% of a C12-15 alkyl methacrylate, preferably LMA; (f) 2% to 19.8% by weight of a C16-20 alkyl methacrylate, preferably SMA, and (g) 0% to 1% by weight of styrene monomer and 20% by weight to 40% by weight of a polyalkyl (meth)acrylate polymer, wherein the total amount of component (e) and component (f) is 20% by weight or less. The present invention relates to an additive composition comprising:

[0059] A second object of the present invention is to (A) 60% to 80% by weight of a base oil, and (B) a monomer of: (a) 9% to 12% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 1% by weight of methyl methacrylate; (c) 60% to 70% by weight of n-butyl methacrylate; (d) 0% by weight to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2 wt% to 18 wt% of a C12-15 alkyl methacrylate; (f) 2% to 19.8% by weight of a C16-20 alkyl methacrylate, and (g) 0% to 1% by weight of styrene monomer 20% by weight to 40% by weight of a polyalkyl (meth)acrylate polymer, wherein the total amount of component (e) and component (f) is 20% by weight or less. The present invention relates to an additive composition comprising:

[0060] The content of each of the components (A) and (B) is based on the total composition of the additive composition.

[0061] In certain embodiments, the proportions of components (A) and (B) add up to 100% by weight.

[0062] The content of each of the components (a), (b), (c), (d), (e), (f) and (g) is based on the total composition of the polyalkyl(meth)acrylate polymer.

[0063] In certain embodiments, the proportions of components (a), (b), (c), (d), (e), (f) and (g) total 100% by weight.

[0064] The base oils used in the additive composition include oils of lubricating viscosity, including natural and synthetic oils, oils derived from hydrocracking, hydrogenation and hydrofinishing, unrefined oils, refined oils, rerefined oils or mixtures thereof.

[0065] Base oils may also be defined as specified by the American Petroleum Institute (API) (see Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, April 2008, Section 1.3, Subheading 1.3, "Base Stock Categories").

[0066] API currently defines five groups of lubricant stocks (API 1509, Annex E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, September 2011). Groups I, II, and III are mineral oils classified by the amount of saturates and sulfur they contain and their viscosity index; Group IV is polyalphaolefins; and Group V is everything else, including ester oils, for example. The ester oils that can be used in accordance with the present invention are preferably selected from the group consisting of Plastomoll DNA, DIOS, and mixtures thereof, with DIOS being even more preferred. The following table shows these API classifications:

[0067] [Table 1]

[0068] The kinematic viscosity (KV) at 100°C of a suitable non-polar base oil used to prepare the additive composition or lubricating composition according to the present invention 100 ) is preferably 3 mm in accordance with ASTM D445 2 / s~10mm 2 / s range, more preferably 4 mm 2 / s~8mm 2 / s range.

[0069] Further base oils that can be used in accordance with the present invention are Group II-III Fischer-Tropsch derived base oils.

[0070] Fischer-Tropsch derived base oils are known in the art. The term "Fischer-Tropsch derived" means that the base oil is or is derived from a synthetic product of the Fischer-Tropsch process. Fischer-Tropsch derived base oils are sometimes referred to as GTL (Gas-To-Liquids) base oils. Suitable Fischer-Tropsch derived base oils that can be advantageously used as the base oil in the lubricating compositions of the present invention are, for example, those disclosed in EP 0 776 959 A, EP 0 668 342 A, WO 97 / 21788, WO 00 / 15736, WO 00 / 14188, WO 00 / 14187, WO 00 / 14183, WO 00 / 14179, WO 00 / 08115, WO 99 / 41332, EP 1 029 029, WO 01 / 18156, WO 01 / 57166 and WO 2013 / 189951.

[0071] API Group III oils are commonly used, especially for 0W and 5W engine oil formulations.

[0072] The additive composition of the present invention preferably contains 70% by weight to 75% by weight of a base oil (component (A)) and 25% by weight to 30% by weight of a polyalkyl (meth)acrylate polymer (component (B)), based on the total weight of the additive composition.

[0073] The third object of the present invention is to (A) 75% by weight to 99.5% by weight of a base oil; (B) a monomer of: (a) 5% to 15% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 2% by weight of methyl methacrylate; (c) 45% to 80% by weight of n-butyl methacrylate; (d) 0% by weight to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2 wt% to 18 wt% of a C12-15 alkyl methacrylate; (f) 2% to 19.8% by weight of a C16-20 alkyl methacrylate, and (g) 0% to 2% by weight of styrene monomer 0.5% by weight to 10% by weight of a polyalkyl(meth)acrylate-based polymer, wherein the total of component (e) and component (f) is 20% by weight or less; and (C) 0% to 15% by weight of one or more further additives The present invention relates to a lubricating oil composition comprising:

[0074] A third object of the present invention is to (A) 75% by weight to 99.5% by weight of a base oil; (B) a monomer of: (a) 6% to 12% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 1% by weight of methyl methacrylate; (c) 45% to 70% by weight of n-butyl methacrylate; (d) 0% by weight to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2 wt% to 18 wt% of a C12-15 alkyl methacrylate; (f) 2% to 19.8% by weight of a C16-20 alkyl methacrylate, and (g) 0% to 1% by weight of styrene monomer 0.5% by weight to 10% by weight of a polyalkyl(meth)acrylate-based polymer, wherein the total of component (e) and component (f) is 20% by weight or less; and (C) 0% to 15% by weight of one or more further additives The present invention relates to a lubricating oil composition comprising:

[0075] A third object of the present invention is to (A) 75% by weight to 99.5% by weight of a base oil; (B) a monomer of: (a) 9% to 12% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 1% by weight of methyl methacrylate; (c) 60% to 70% by weight of n-butyl methacrylate; (d) 0% by weight to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2 wt% to 18 wt% of a C12-15 alkyl methacrylate; (f) 2% to 19.8% by weight of a C16-20 alkyl methacrylate, and (g) 0% to 1% by weight of styrene monomer 0.5% by weight to 10% by weight of a polyalkyl(meth)acrylate polymer, wherein the total of component (e) and component (f) is 20% by weight or less; and (C) 0% to 15% by weight of one or more further additives The present invention relates to a lubricating oil composition comprising:

[0076] The content of each of the components (A), (B) and (C) is based on the total composition of the lubricating oil composition.

[0077] The content of each of the components (a), (b), (c), (d), (e), (f) and (g) is based on the total composition of the polyalkyl(meth)acrylate polymer.

[0078] In certain embodiments, the proportions of components (a), (b), (c), (d), (e), (f) and (g) total 100% by weight.

[0079] The lubricating oil composition according to the invention may also contain, as component (C), further additives selected from the group consisting of conventional VI improvers, dispersants, antifoam agents, detergents, antioxidants, pour point depressants, antiwear additives, extreme pressure additives, friction modifiers, anticorrosion additives, dyes and mixtures thereof.

[0080] Conventional VI improvers include hydrogenated styrene-diene copolymers (HSD, U.S. Pat. Nos. 4,116,917, 3,772,196 and 4,788,316), especially based on butadiene and isoprene, and olefin copolymers, especially of the poly(ethylene-co-propylene) type (OCPs, K. Marsden: "Literature Review of OCP Viscosity Modifiers", Lubrication Science 1 (1988), 265), which can often be present in N / O-functional form with dispersing action, or PAMA, which is usually present in N-functional form with advantageous additive properties (boosters) as dispersants, wear protection additives and / or friction modifiers (German Patent Application Publication No. 1520696 by Rohm and Haas, WO 2006 / 007934 by RohMax Additives).

[0081] The synthesis of VI improvers and pour point improvers for lubricating oils, in particular motor oils, is described in detail, for example, in T. Mang, W. Dresel (eds.): "Lubricants and Lubrication", Wiley-VCH, Weinheim 2001; R.M. Mortier, S.T. Orszulik (eds.): "Chemistry and Technology of Lubricants", Blackie Academic & Professional, London 1992, or J. Bartz: "Additive fur Schmierstoffe", Expert-Verlag, Renningen-Malmsheim 1994.

[0082] Suitable dispersants include poly(isobutylene) derivatives such as poly(isobutylene) succinimide (PIBSI), including borated PIBSI, and ethylene-propylene oligomers with N / O functionality.

[0083] Dispersants (including borated dispersants) are preferably used in an amount of 0 to 5 wt %, based on the total weight of the lubricating oil composition.

[0084] Suitable antifoaming agents include silicone oils, fluorosilicone oils, fluoroalkyl ethers, and the like.

[0085] The antifoaming agent is preferably used in an amount of 0.005 to 0.1% by weight, based on the total amount of the lubricating oil composition.

[0086] Preferred detergents include metal-containing compounds such as phenoxides; salicylates; thiophosphonates, especially thiopyrophosphonates, thiophosphonates, and phosphonates; sulfonates, and carbonates. These compounds may contain metals, especially calcium, magnesium, and barium. These compounds may be used preferably in neutral or overbased form.

[0087] The detergent is preferably used in an amount of 0.2 to 1% by weight, based on the total amount of the lubricating oil composition.

[0088] Suitable antioxidants include, for example, phenolic antioxidants and amine antioxidants.

[0089] Examples of phenolic antioxidants include octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-t-butylphenol); 4,4'-bis(2-methyl-6-t-butylphenol); 2,2'-methylenebis(4-ethyl-6-t-butylphenol); 2,2'-methylenebis(4-methyl -6-t-butylphenol;4,4'-butylidenebis(3-methyl-6-t-butylphenol);4,4'-isopropylidenebis(2,6-di-t-butylphenol);2,2'-methylenebis(4-methyl-6-nonylphenol);2,2'-isobutylidenebis(4,6-dimethylphenol);2,2'-methylenebis(4-methyl-6-cyclohexylphenol);2,6-di-t-butyl-4-methylphenol;2, 6-Di-t-butyl-4-ethyl-phenol;2,4-dimethyl-6-t-butylphenol;2,6-di-t-amyl-p-cresol;2,6-di-t-butyl-4-(N,N'-dimethylaminomethylphenol);4,4'-thiobis(2-methyl-6-t-butylphenol);4,4'-thiobis(3-methyl-6-t-butylphenol);2,2'-thiobis(4-methyl-6-t-butylphenol);Bis(3-methyl-4-hydroxybenzoyl)phenol Examples of antioxidants include bis(3,5-di-t-butylbenzyl)sulfide, bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, n-octyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, n-octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, and 2,2'-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]. Among these, bisphenol-based antioxidants and ester group-containing phenol-based antioxidants are particularly preferred.

[0090] Examples of the amine antioxidants include monoalkyldiphenylamines such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamines such as 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine; polyalkyldiphenylamines such as tetrabutyldiphenylamine and tetrahexyldiphenylamine; naphthylamines, specifically alpha-naphthylamine, phenyl-alpha-naphthylamine, and further alkyl-substituted phenyl-alpha-naphthylamines, such as butylphenyl-alpha-naphthylamine, pentylphenyl-alpha-naphthylamine, hexylphenyl-alpha-naphthylamine, heptylphenyl-alpha-naphthylamine, octylphenyl-alpha-naphthylamine, nonylphenyl-alpha-naphthylamine, etc. Among these, diphenylamine is preferred over naphthylamine in terms of its antioxidant effect.

[0091] Suitable antioxidants may further be selected from the group consisting of sulfur- and phosphorus-containing compounds, such as metal dithiophosphates, e.g., zinc dithiophosphate (ZnDTP), "OOS triesters" = reaction products of dithiophosphoric acids with activated double bonds from olefins, cyclopentadiene, norbornadiene, α-pinene, polybutenes, acrylic esters, maleic esters (ashless combustion); organic sulfur compounds, e.g., dialkyl sulfides, diaryl sulfides, polysulfides, modified thiols, thiophene derivatives, xanthates, thioglycols, thioaldehydes, sulfur-containing carboxylic acids; heterocyclic sulfur / nitrogen compounds, in particular dialkyldimercaptothiadiazoles, 2-mercaptobenzimidazoles; zinc bis(dialkyldithiocarbamates) and methylene bis(dialkyldithiocarbamates); organic phosphorus compounds, e.g., triaryl and trialkyl phosphites; organic copper compounds and overbased calcium- and magnesium-based phenoxides and salicylates.

[0092] The antioxidant is used in an amount of 0 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total amount of the lubricating oil composition.

[0093] Examples of pour point depressants include ethylene-vinyl acetate copolymers, chlorinated paraffin-naphthalene condensates, chlorinated paraffin-phenol condensates, polymethacrylates, polyalkylstyrenes, etc. Polymethacrylates having a mass average molecular weight of 5,000 to 50,000 g / mol are preferred.

[0094] The amount of pour point depressant is preferably 0.1 to 5% by weight, based on the total amount of the lubricating oil composition.

[0095] Preferred antiwear and extreme pressure additives include sulfur-containing compounds such as zinc dithiophosphate, diC 3~12zinc alkyldithiophosphates (ZnDTP), zinc phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, disulfides, sulfurized olefins, sulfurized fats and oils, sulfurized esters, thiocarbonates, thiocarbamates, polysulfides, etc.; phosphorus-containing compounds such as phosphites, phosphates, for example, trialkyl phosphates, triaryl phosphates, for example, tricresyl phosphate, amine-neutralized mono- and dialkyl phosphates, ethoxylated mono- and dialkyl phosphates, phosphonates, phosphines, amine salts or metal salts of these compounds, etc.; sulfur- and phosphorus-containing antiwear agents such as thiophosphites, thiophosphates, thiophosphonates, amine salts or metal salts of these compounds, etc.

[0096] The antiwear agent may be present in an amount of 0 to 3 wt %, preferably 0.1 to 1.5 wt %, more preferably 0.5 to 0.9 wt %, based on the total amount of the lubricating oil composition.

[0097] The friction modifiers used may include mechanically active compounds such as molybdenum disulfide, graphite (including fluorinated graphite), poly(trifluoroethylene), polyamides, polyimides; compounds that form adsorption layers such as long-chain carboxylic acids, fatty acid esters, ethers, alcohols, amines, amides, imides; compounds that form layers by tribochemical reaction such as saturated fatty acids, phosphoric and thiophosphate esters, xanthates, sulfurized fatty acids; compounds that form polymeric layers such as ethoxylated dicarboxylic acid partial esters, dialkyl phthalates, methacrylates, unsaturated fatty acids, sulfurized olefins or organometallic compounds such as molybdenum compounds (molybdenum dithiophosphates and molybdenum dithiocarbamates MoDTC) and their combinations with ZnDTP, copper-containing organic compounds.

[0098] The friction modifier may be used in an amount of 0 to 6% by weight, preferably 0.05 to 4% by weight, and more preferably 0.1 to 2% by weight, based on the total amount of the lubricating oil composition.

[0099] Some of the compounds listed above may serve multiple functions: for example, ZnDTP is primarily an antiwear and extreme pressure additive, but also has antioxidant and corrosion inhibitor (here, metal passivator / deactivator) properties.

[0100] The above-mentioned additives are described in detail, inter alia, in T. Mang, W. Dresel (eds.): "Lubricants and Lubrication", Wiley-VCH, Weinheim 2001; RM Mortier, ST Orszulik (eds.): "Chemistry and Technology of Lubricants".

[0101] Preferably, the total concentration of the one or more additives (C) is from 0.05% to 15% by weight, more preferably from 3% to 10% by weight, based on the total weight of the lubricating oil composition.

[0102] The invention is illustrated by the following non-limiting examples. [Example]

[0103] Abbreviation AMA alkyl methacrylate Group II / III oil Light process oil with KV100 of 1cSt BMA n-butyl methacrylate C1 AMA C1-Alkyl Methacrylate = Methyl Methacrylate (MMA) C4 AMA C4-Alkyl methacrylate = n-Butyl methacrylate (BMA) C12-15 AMA C12-15 Alkyl Methacrylate Mixture C16~18 AA C16~18 Alkyl Acrylate Mixture 100N oil: Group II base oil with a KV100 of 4 cSt DDM Dodecanethiol HTHS80 High temperature high shear viscosity at 80°C measured according to CEC L-036 HTHS100 High temperature high shear viscosity at 100°C measured according to CEC L-036 HTHS150 High temperature high shear viscosity at 150°C measured according to CEC L-036 IDMA Isodecyl methacrylate containing up to 15% by weight of C11 alkyl methacrylate KV Kinematic viscosity measured according to ASTM D445 KV40 Kinematic viscosity at 40°C measured according to ISO 3104 KV100 Kinematic viscosity at 100°C measured according to ISO3104 LMA Lauryl methacrylate, 73% C12, 27% C14, all linear MM Macromonomer MMA Methyl methacrylate M n number average molecular weight M w Weight average molecular weight NB3020 Nexbase® 3020, a Group III base oil manufactured by Neste with a KV100 of 2.2 cSt NB3043 Nexbase® 3043, a Group III base oil manufactured by Neste with a KV100 of 4.3 cSt OLOA 9728X DI package for PCMO available from Oronite PCMO Passenger Car Motor Oil PDI polydispersity index SMA C16-20 alkyl methacrylate, all linear VI Viscosity index measured according to ISO 2909

[0104] Test Method The polyalkyl(meth)acrylate-based polymers according to the present invention and comparative examples were characterized with respect to their molecular weight and PDI.

[0105] Molecular weights were determined by size exclusion chromatography (SEC) using commercially available polymethyl methacrylate (PMMA) standards. The determination is carried out by gel permeation chromatography (flow rate: 1 mL / min; injection volume: 100 μl) using THF as the eluent.

[0106] Columns: Five SDV columns 8 x 300 mm, each 8 x 50 mm (PSS, Mainz) One solvent peak separation column 8 x 100 mm (Shodex) Number Type Dimensions Serial number Precolumn SDV 10μ 8×50mm 91121224 1 SDV LXL 10μ 8×300mm 6013101 2 SDV LinL 10μ 8×300mm 6082302 3 SDV 100Å 10μ 8×300mm 0071401 4 SDV 100Å 10μ 8×300mm 0070508 5 KF-800D 8×100mm 2007012

[0107] Equipment: Agilent 1100 Series Pump G1310A PSS SECcurity Inline-Degaser 409-0024 Agilent 1260 Series Autosampler G1329B Agilent 1260 Series UV Detector G1314B Agilent 1100 Series RI Detector G1362A Agilent 1100 Series Control Module G1323B Techlab Column Oven K-5

[0108] Oven temperature: 35℃ Eluent: tetrahydrofuran The eluent is continuously distilled and circulated by a pump. Flow rate: 1ml / min Injection volume: 100μl Detection: RI: Temperature 35℃ UV: Wavelength 239nm Delay volume: 0.175 ml (between UV and RI signals) Software: PSS WinGPC Software Concentration sample solution: 2g / L (Mw>106: 1g / L...0.5g / L) Standard: PMMA (e.g. PSS (Mainz) or Polymer Laboratories) Concentration standard solution: 1 g / l (if Mw>106: 0.5 g / l, if Mw>2 x 106: 0.25 g / l) (narrow distribution) Internal standard: 1,2-dichlorobenzene → 0.2 μL to 99.8 μL sample

[0109] Lubricating oil compositions containing the polyalkyl(meth)acrylate-based polymers according to the present invention and comparative examples were characterized for kinematic viscosity at 40°C (KV40) and 100°C (KV100) according to ASTM D445, viscosity index (VI) according to ASTM D2270, and pour point according to ASTM D-5950.

[0110] They were further characterized by Brookfield viscosity at −40°C according to DIN 51398, CCS apparent viscosity at −30°C (Cold-Cranking Simulator) according to ASTM D5293, and yield stress at −35°C according to ASTM D-4684 (Mini Rotational Viscometer-MRV-TP1).

[0111] To indicate the shear stability of the lubricating oil compositions, the PSSI (Permanent Shear Stability Index) was calculated according to ASTM D6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index) based on data measured according to ASTM D-445 / CEC L-45-A-99 ("Kegelrollenlager", KRL, 60°C, 5KN, 1475+ / -25 rpm for 20 hours).

[0112] The shear stability of the lubricating oil compositions was further measured according to ASTM D-445 / CEC-L-14 (Bosch injector, 30 cycles) and the PSSI was calculated according to ASTM D6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index).

[0113] Synthesis of hydroxylated hydrogenated polybutadiene The prepared macroalcohols have an average molar mass M n = 4750 g / mol.

[0114] The macroalcohols were synthesized by anionic polymerization of 1,3-butadiene with butyllithium at 20–45 °C. Once the desired degree of polymerization was reached, the reaction was quenched by adding propylene oxide, and the lithium was removed by precipitation with methanol. The polymer was then hydrogenated under a hydrogen atmosphere in the presence of a noble metal catalyst at temperatures up to 140 °C and 200 bar pressure. After hydrogenation, the noble metal catalyst was removed, and the organic solvent was stripped under reduced pressure. Finally, the polymer content was diluted to 70 wt% using base oil NB3020.

[0115] The vinyl content of the macroalcohol was 61%, the hydrogenation level was greater than 99%, and the OH functionality was greater than 98%, as determined by H-NMR (nuclear resonance spectroscopy).

[0116] Synthesis of macromonomer (MM) In a 2 L stirred apparatus equipped with a saber stirrer, an air inlet tube, a thermocouple with a control valve, a heating mantle, a column with a random packing of 3 mm wire spirals, a vapor divider, an upper thermometer, a reflux condenser, and a base condenser, 1000 g of the above macroalcohol was dissolved in 450 g of methyl methacrylate (MMA) by stirring at 60 °C. 20 ppm of 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 200 ppm of hydroquinone monomethyl ether were added to the solution. After heating to MMA reflux (bottom temperature approximately 110 °C) with air passing through for stabilization, approximately 20 g of MMA was distilled off for azeotropic drying. After cooling to 95 °C, 0.30 g of LiOCH3 was added and the mixture was heated to reflux. After approximately 1 hour of reaction time, the maximum temperature dropped to approximately 64 °C due to methanol formation. The methanol / MMA azeotrope formed was continuously distilled off until a constant maximum temperature of about 100 °C was again established. At this temperature, the mixture was allowed to react for another hour. The bulk of the MMA was removed under reduced pressure for further workup. Insoluble catalyst residues were removed by pressure filtration (Seitz T1000 depth filter). Therefore, the content of NB3020 "entrained" during the copolymer synthesis, which is further described below, was taken into account.

[0117] Synthesis of Example 1 62.70 g of NB3043, 26.00 g of Group II / III oil, 28.40 g of MM (70% in Nexbase 3020), 7.00 g of LMA, 8.70 g of SMA, 0.10 g of styrene, 61.20 g of BMA, and 0.30 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.16 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 7.00 g LMA, 8.80 g SMA, 0.20 g styrene, 61.20 g BMA, 0.6 g MMA, 57.0 g NB3043, and 20.8 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.27 g tert-butyl peroxy-2-ethylhexanoate and 2.45 g NB3043 was added over 240 minutes.

[0118] 240 minutes after the start of the reaction, an additional 87.5 g of NB3043 was added over 120 minutes. Concurrently, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 g of LMA and 2.57 g of SMA was added to the heel to help reduce the amount of BMA remaining.

[0119] The mixture was stirred overnight at 90° C. The next day, 256.90 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0120] Synthesis of Example 2 62.70 g of NB3043, 26.00 g of Group II / III oil, 28.40 g of MM (70% in Nexbase 3020), 15.70 g of SMA, 0.10 g of styrene, 61.20 g of BMA, and 0.30 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.16 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 15.80 g SMA, 0.20 g styrene, 61.20 g BMA, 0.60 g MMA, 57.00 g NB3043, and 20.80 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.27 g tert-butyl peroxy-2-ethylhexanoate and 2.45 g NB3043 was added over 240 minutes.

[0121] 240 minutes after the start of the reaction, an additional 87.50 g of NB3043 was added over 120 minutes. Concurrently, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 g of LMA and 2.60 g of SMA was added to the heel to help reduce the amount of BMA remaining.

[0122] The mixture was stirred overnight at 90° C. The next day, 256.90 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0123] Synthesis of Example 3 62.60 g of NB3043, 26.00 g of Group II / III oil, 29.00 g of MM (70% in Nexbase 3020), 11.30 g of LMA, 4.80 g of SMA, 0.10 g of styrene, 60.60 g of BMA, and 0.30 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.17 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 11.30 g LMA, 4.80 g SMA, 0.20 g styrene, 60.60 g BMA, 0.60 g MMA, 56.90 g NB3043, and 20.80 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.27 g tert-butyl peroxy-2-ethylhexanoate and 2.45 g NB3043 was added over 240 minutes.

[0124] 240 minutes after the start of the reaction, an additional 87.50 g of NB3043 was added over 120 minutes. Concurrently, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 g of LMA and 2.60 g of SMA was added to the heel to help reduce the amount of BMA remaining.

[0125] The mixture was stirred overnight at 90° C. The next day, 256.90 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0126] Synthesis of Example 4 64.20 g of NB3043, 26.00 g of Group II / III oil, 23.30 g of MM (70% in Nexbase 3020), 9.09 g of IDMA, 16.40 g of SMA, 0.10 g of styrene, 55.10 g of BMA, and 0.20 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.15 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 8.92 g IDMA, 16.10 g SMA, 0.20 g styrene, 54.10 g BMA, 0.20 g MMA, 58.30 g NB3043, and 21.30 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.28 g tert-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over 240 minutes.

[0127] 240 minutes after the start of the reaction, an additional 88.40 g of NB3043 was added over 120 minutes. Concurrently, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 g of LMA and 2.60 g of SMA was added to the heel to help reduce the amount of BMA remaining.

[0128] The mixture was stirred overnight at 90° C. The next day, 259.50 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0129] Synthesis of Example 5 62.70 g of NB3043, 26.00 g of Group II / III oil, 28.40 g of MM (70% in Nexbase 3020), 12.70 g of LMA, 3.10 g of SMA, 0.10 g of styrene, 61.20 g of BMA, and 0.30 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.16 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 12.70 g LMA, 3.10 g SMA, 0.20 g styrene, 61.20 g BMA, 0.60 g MMA, 57.00 g NB3043, and 20.80 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.27 g tert-butyl peroxy-2-ethylhexanoate and 2.45 g NB3043 was added over 240 minutes.

[0130] 240 minutes after the start of the reaction, an additional 87.50 g of NB3043 was added over 120 minutes. Concurrently, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 g of LMA and 2.60 g of SMA was added to the heel to help reduce the amount of BMA remaining.

[0131] The mixture was stirred overnight at 90° C. The next day, 256.90 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0132] Synthesis of Example 6 (Comparative Example) 62.70 g of NB3043, 25.90 g of Group II / III oil, 27.90 g of MM (70% in Nexbase 3020), 1.20 g of LMA, 22.00 g of SMA, 0.10 g of styrene, 54.00 g of BMA, and 0.30 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.16 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 1.20 g LMA, 22.00 g SMA, 0.20 g styrene, 54.00 g BMA, 0.6 g MMA, 57.1 g NB3043, and 20.8 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.27 g tert-butyl peroxy-2-ethylhexanoate and 2.46 g NB3043 was added over 240 minutes.

[0133] After 240 minutes from the start of the reaction, an additional 87.5 g of NB3043 was added over 120 minutes, and simultaneously, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over 180 minutes.

[0134] The mixture was stirred overnight at 90° C. The next day, 256.90 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0135] Synthesis of Example 7 (Comparative Example) 62.70 g of NB3043, 25.90 g of Group II / III oil, 27.90 g of MM (70% in Nexbase 3020), 8.58 g of IDMA, 1.20 g of LMA, 22.00 g of SMA, 0.20 g of styrene, 45.40 g of BMA, and 0.20 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.16 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 8.58 g IDMA, 1.20 g LMA, 22.00 g SMA, 0.20 g styrene, 45.40 g BMA, 0.60 g MMA, 57.10 g NB3043, and 20.80 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.27 g tert-butyl peroxy-2-ethylhexanoate and 2.46 g NB3043 was added over 240 minutes.

[0136] After 240 minutes from the start of the reaction, an additional 87.50 g of NB3043 was added over 120 minutes, and simultaneously, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over 180 minutes.

[0137] The mixture was stirred overnight at 90° C. The next day, 256.90 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0138] Synthesis of Example 8 (Comparative Example) 62.70 g of NB3043, 25.90 g of Group II / III oil, 27.90 g of MM (70% in Nexbase 3020), 12.87 g of IDMA, 1.20 g of LMA, 22.00 g of SMA, 0.10 g of styrene, 41.10 g of BMA, and 0.20 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.16 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 12.87 g IDMA, 1.20 g LMA, 22.00 g SMA, 0.20 g styrene, 41.10 g BMA, 0.60 g MMA, 57.10 g NB3043, and 20.90 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.27 g tert-butyl peroxy-2-ethylhexanoate and 2.46 g NB3043 was added over 240 minutes.

[0139] After 240 minutes from the start of the reaction, an additional 87.50 g of NB3043 was added over 120 minutes, and simultaneously, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over 180 minutes.

[0140] The mixture was stirred overnight at 90° C. The next day, 256.90 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0141] Synthesis of Example 9 (Comparative Example) 65.30 g of NB3043, 26.90 g of Group II / III oil, 27.90 g of MM (70% in Nexbase 3020), 13.60 g of LMA, 7.00 g of C16-18 AA, 0.10 g of styrene, 60.00 g of BMA, and 0.30 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.20 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 13.60 g LMA, 0.20 g styrene, 60.00 g BMA, 0.60 g MMA, 54.50 g NB3043, and 19.90 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.26 g tert-butyl peroxy-2-ethylhexanoate and 2.35 g NB3043 was added over 240 minutes.

[0142] After 240 minutes from the start of the reaction, an additional 87.50 g of NB3043 was added over 120 minutes, and simultaneously, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over 180 minutes.

[0143] The mixture was stirred overnight at 90° C. The next day, 257.00 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0144] Synthesis of Example 10 62.80 g of NB3043, 26.00 g of Group II / III oil, 28.40 g of MM (70% in Nexbase 3020), 10.63 g of IDMA, 10.10 g of LMA, 7.40 g of SMA, 0.10 g of styrene, 49.00 g of BMA, and 0.20 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.95 g of a 10% solution of tert-butylperoxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 10.63 g IDMA, 10.10 g LMA, 7.40 g SMA, 0.30 g styrene, 49.00 g BMA, 0.20 g MMA, 0.16 g tert-butylperoxy-2-ethylhexanoate in 1.40 g NB3043, 56.90 g NB3043, and 20.80 g Group II / III oil over 180 minutes.

[0145] 240 minutes after the start of the reaction, another 87.50 g of NB3043 containing 0.35 g of tert-butyl peroxy-2-ethylhexanoate in 3.15 g of NB3043 was added over 180 minutes. 120 minutes after the addition, 0.35 g of tert-butyl peroxy-2-ethylhexanoate was added.

[0146] The mixture was stirred overnight at 90° C. The next day, 256.20 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0147] Synthesis of Example 11 63.20 g of NB3043, 25.00 g of Group II / III oil, 17.40 g of MM (70% in Nexbase 3020), 10.11 g of IDMA, 5.30 g of LMA, 12.20 g of SMA, 0.10 g of styrene, 53.40 g of BMA, and 0.20 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.87 g of a 10% solution of tert-butylperoxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 10.11 g IDMA, 5.30 g LMA, 12.30 g SMA, 0.30 g styrene, 53.40 g BMA, 0.20 g MMA, 0.16 g tert-butylperoxy-2-ethylhexanoate in 1.47 g NB3043, 59.70 g NB3043, and 21.80 g Group II / III oil over 180 minutes.

[0148] 240 minutes after the start of the reaction, another 87.50 g of NB3043 containing 0.35 g of tert-butyl peroxy-2-ethylhexanoate in 3.15 g of NB3043 was added over 180 minutes. 120 minutes after the addition, 0.35 g of tert-butyl peroxy-2-ethylhexanoate was added.

[0149] The mixture was stirred overnight at 90° C. The next day, 256.20 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0150] Synthesis of Example 12 47.80 g of NB3043, 40.30 g of Group II / III oil, 17.40 g of MM (70% in Nexbase 3020), 21.87 g of IDMA, 5.30 g of LMA, 12.20 g of SMA, 0.10 g of styrene, 53.40 g of BMA, and 0.20 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.87 g of a 10% solution of tert-butylperoxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.10 g MM (70% in NB3020), 10.11 g IDMA, 5.30 g LMA, 12.30 g SMA, 0.30 g styrene, 53.40 g BMA, 0.20 g MMA, 0.16 g tert-butylperoxy-2-ethylhexanoate in 1.47 g NB3043, 59.70 g NB3043, and 21.80 g Group II / III oil over 180 minutes.

[0151] 240 minutes after the start of the reaction, another 87.50 g of NB3043 containing 0.35 g of tert-butyl peroxy-2-ethylhexanoate in 3.15 g of NB3043 was added over 180 minutes. 120 minutes after the addition, 0.35 g of tert-butyl peroxy-2-ethylhexanoate was added.

[0152] The mixture was stirred overnight at 90° C. The next day, 256.20 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0153] Synthesis of Example 13 61.39 g of NB3043, 25.46 g of Group II / III oil, 22.41 g of MM (70% in Nexbase 3020), 0.17 g of LMA, 17.32 g of SMA, 7.33 g of IDMA, 0.12 g of styrene, 53.03 g of BMA, and 0.15 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.00 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.09 g MM (70% in NB3020), 0.18 g LMA, 17.32 g SMA, 8.75 g IDMA, 0.23 g styrene, 53.03 g BMA, 0.19 g MMA, 55.91 g NB3043, and 21.34 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.28 g tert-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over 240 minutes.

[0154] After 240 minutes from the start of the reaction, an additional 86.83 g of NB3043 was added over 90 minutes along with 0.35 g of tert-butylperoxy-2-ethylhexanoate.

[0155] The mixture was stirred overnight at 90° C. The next day, 260.49 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0156] Synthesis of Example 14 61.39 g of NB3043, 25.46 g of Group II / III oil, 22.42 g of MM (70% in Nexbase 3020), 0.17 g of LMA, 17.32 g of SMA, 10.99 g of IDMA, 0.12 g of styrene, 48.64 g of BMA, and 0.15 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.00 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.07 g MM (70% in NB3020), 0.18 g LMA, 17.33 g SMA, 13.13 g IDMA, 0.23 g styrene, 48.66 g BMA, 0.19 g MMA, 55.91 g NB3043, and 21.34 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.28 g tert-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over 240 minutes.

[0157] After 240 minutes from the start of the reaction, an additional 86.85 g of NB3043 was added over 90 minutes along with 0.35 g of tert-butylperoxy-2-ethylhexanoate.

[0158] The mixture was stirred overnight at 90° C. The next day, 259.95 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0159] Synthesis of Example 15 61.39 g of NB3043, 25.46 g of Group II / III oil, 22.41 g of MM (70% in Nexbase 3020), 5.25 g of LMA, 12.25 g of SMA, 7.33 g of IDMA, 0.12 g of styrene, 53.03 g of BMA, and 0.15 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.00 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.09 g MM (70% in NB3020), 5.25 g LMA, 12.25 g SMA, 8.75 g IDMA, 0.23 g styrene, 53.03 g BMA, 0.19 g MMA, 55.91 g NB3043, and 21.34 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.28 g tert-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over 240 minutes.

[0160] After 240 minutes from the start of the reaction, an additional 86.83 g of NB3043 was added over 90 minutes along with 0.35 g of tert-butylperoxy-2-ethylhexanoate.

[0161] The mixture was stirred overnight at 90° C. The next day, 260.49 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes, after which the batch was transferred to a glass bottle.

[0162] Synthesis of Example 16 61.39 g of NB3043, 25.46 g of Group II / III oil, 22.42 g of MM (70% in Nexbase 3020), 5.25 g of LMA, 12.25 g of SMA, 10.99 g of IDMA, 0.12 g of styrene, 48.64 g of BMA, and 0.15 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.00 g of a 10% solution of tert-butylperoxy-2-ethylhexanoate in NB3043, followed by the addition of a mixture of 0.07 g MM (70% in NB3020), 5.25 g LMA, 12.25 g SMA, 13.13 g IDMA, 0.23 g styrene, 48.66 g BMA, 0.19 g MMA, 55.91 g NB3043, and 21.34 g Group II / III oil over 180 minutes. Concurrently, a second mixture of 0.28 g tert-butylperoxy-2-ethylhexanoate and 2.51 g NB3043 was added over 240 minutes.

[0163] After 240 minutes from the start of the reaction, an additional 86.65 g of NB3043 was added over 90 minutes along with 0.35 g of tert-butylperoxy-2-ethylhexanoate.

[0164] The mixture was stirred overnight at 90° C. The next day, 259.95 g of NB3043 was added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0165] Synthesis of Example 17 86.89 g of 100N oil, 22.41 g of MM (70% in Nexbase 3020), 0.17 g of LMA, 17.32 g of SMA, 1.67 g of IDMA, 0.12 g of styrene, 60.12 g of BMA, and 0.15 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.00 g of a 10% solution of tert-butylperoxy-2-ethylhexanoate in 100 N oil, followed by the addition of a mixture of 0.09 g MM (70% in NB3020), 0.18 g LMA, 17.32 g SMA, 1.66 g IDMA, 0.23 g styrene, 60.12 g BMA, 0.19 g MMA, and 77.25 g 100 N oil over 180 min. Concurrently, a second mixture of 0.28 g tert-butylperoxy-2-ethylhexanoate and 2.51 g NB3043 was added over 240 min.

[0166] 240 minutes after the start of the reaction, an additional 87.20 g of 100N oil was added over 90 minutes along with 0.35 g of tert-butylperoxy-2-ethylhexanoate.

[0167] The mixture was stirred overnight at 90° C. The next day, 261.59 g of 100N oil was added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0168] Synthesis of Example 18 86.89 g of 100N oil, 24.94 g of MM (70% in Nexbase 3020), 0.18 g of LMA, 17.51 g of SMA, 1.68 g of IDMA, 0.13 g of styrene, 58.11 g of BMA, and 0.16 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.00 g of a 10% solution of tert-butylperoxy-2-ethylhexanoate in 100 N oil, followed by the addition of a mixture of 5.26 g MM (70% in NB3020), 0.18 g LMA, 17.10 g SMA, 1.64 g IDMA, 0.22 g styrene, 56.76 g BMA, 0.19 g MMA, and 77.20 g 100 N oil over 180 min. Concurrently, a second mixture of 0.28 g tert-butylperoxy-2-ethylhexanoate and 2.56 g NB3043 was added over 240 min.

[0169] 240 minutes after the start of the reaction, an additional 87.78 g of 100N oil was added over 90 minutes along with 0.35 g of tert-butylperoxy-2-ethylhexanoate.

[0170] The mixture was stirred overnight at 90° C. The next day, 263.34 g of 100N oil was added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0171] Synthesis of Example 19 86.89 g of 100N oil, 24.67 g of MM (70% in Nexbase 3020), 0.17 g of LMA, 17.16 g of SMA, 1.65 g of IDMA, 0.15 g of styrene, 58.67 g of BMA, and 0.15 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.00 g of a 10% solution of tert-butylperoxy-2-ethylhexanoate in 100 N oil, followed by the addition of a mixture of 0.09 g MM (70% in NB3020), 0.18 g LMA, 17.52 g SMA, 1.68 g IDMA, 0.20 g styrene, 59.92 g BMA, 0.20 g MMA, and 77.25 g 100 N oil over 180 min. Concurrently, a second mixture of 0.28 g tert-butylperoxy-2-ethylhexanoate and 2.51 g NB3043 was added over 240 min.

[0172] 240 minutes after the start of the reaction, an additional 87.36 g of 100N oil was added over 90 minutes along with 0.35 g of tert-butylperoxy-2-ethylhexanoate.

[0173] The mixture was stirred overnight at 90° C. The next day, 262.09 g of 100N oil was added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0174] Synthesis of Example 20 86.89 g of 100N oil, 26.91 g of MM (70% in Nexbase 3020), 0.17 g of LMA, 17.01 g of SMA, 1.63 g of IDMA, 0.13 g of styrene, 57.30 g of BMA, and 0.15 g of MMA were placed in a four-neck glass flask equipped with a stirrer, temperature sensor, nitrogen line, and reflux condenser. The flask was flushed with nitrogen and heated to 90°C. The reaction was then initiated by the addition of 1.00 g of a 10% solution of tert-butylperoxy-2-ethylhexanoate in 100 N oil, followed by the addition of a mixture of 0.09 g MM (70% in NB3020), 0.18 g LMA, 17.72 g SMA, 1.70 g IDMA, 0.22 g styrene, 59.69 g BMA, 0.20 g MMA, and 77.25 g 100 N oil over 180 min. Concurrently, a second mixture of 0.28 g tert-butylperoxy-2-ethylhexanoate and 2.51 g NB3043 was added over 240 min.

[0175] 240 minutes after the start of the reaction, an additional 87.54 g of 100N oil was added over 90 minutes along with 0.35 g of tert-butylperoxy-2-ethylhexanoate.

[0176] The mixture was stirred overnight at 90° C. The next day, 262.61 g of 100N oil was added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0177] The composition of the resulting polyalkyl(meth)acrylate polymer is summarized in Table 1 below.

[0178] [Table 2]

[0179] Unless otherwise specified, the term "%" means % by weight (wt.%).

[0180] Examples 1-5 and 10-20 are in accordance with the present invention. Examples 6-8 are comparative examples because they contain higher SMA contents than the claimed range. Example 9 is comparative because it contains a C16 / 18 alkyl acrylate instead of an alkyl methacrylate.

[0181] Weight average molecular weight M w , number average molecular weight M n Typical characteristics of the resulting polyalkyl(meth)acrylate-based polymers, such as their densities and polydispersity indices (PDIs), are summarized in Table 2 below.

[0182] [Table 3]

[0183] The examples according to the invention exhibited weight average molecular weights ranging from 511,000 g / mol (Example 5) to 870,000 g / mol (Example 18).

[0184] Evaluation of VI improvers in formulations To demonstrate the effect of the polyalkyl(methacrylate)-based polymer of the present invention on the performance of lubricating oil compositions, different formulation examples A were prepared and corresponding values were measured. Formulations using API Group II 100N oil (e.g., Aramco PRIMA) and API Group II 220N oil (e.g., Chevron 220R) as base oils were prepared with fixed amounts of DI package and viscosity modifier concentrations as outlined in Table 3 below. The formulations were targeted to meet the following industry standards / specifications: 5W-30 (SAE J300), 75W-80 (SAE J306), John Deere JD 20 C, Caterpillar TO-4 SAE 30.

[0185] The combined formulation goals are outlined in the second column of Table 4 below.

[0186] The resulting viscosity-modifying additive content was typically 8-12 wt%. Characteristic EO / UTTO compounding properties (KV40, KV100, HTHS150, Brookfield-40, MRV TP1-35, CCS-30, and KV100 (shear)) were measured and are summarized in Table 3.

[0187] [Table 4-1] [Table 4-2]

[0188] [Table 5]

[0189] The results shown in Tables 3a and 3b clearly demonstrate that only lubricating oil compositions containing polymers according to the present invention can meet the stringent requirements posed by combining several industry specifications. They exhibit good wax control (pour point) and excellent low temperature performance (low Brookfield) while maintaining very good shear stability. Examples A1-A5, including Polymer Examples 1-5, achieved pour points of at least -36°C and CCS values of less than 6,600 mPas. The KV100 values of Formulations A1-A5 exceeded the target of 9.3 mm after 30 cycles of Bosch injector shear, meeting the requirements of SAE J300. 2 They also achieved a KV100 > 7.1 mm required to meet the SAE J306 requirements for 75W-80 formulations or to meet the JD20C specification. 2 / s met the more stringent post-shear requirements.

[0190] Comparative Examples A6 to A8 showed significantly lower CCS viscosities despite using the same proportions of heavy base oil. The PSSI and KV100 values after shear were significantly worse and did not meet the stringent requirements.

[0191] The use of Polymer Example 9, in which C16 / 18 alkyl acrylate was used instead of C16 / 18 alkyl methacrylate (see Example 5), resulted in Formulation A9, which met the shear stability requirements but failed to meet the low temperature requirements: the pour point was only -27°C and the formulation was solid at -40°C, i.e., it was not possible to measure the Brookfield viscosity at -40°C.

Claims

1. The following monomers: (a) 6% to 12% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 1% by weight of methyl methacrylate; (c) 45% to 70% by weight of n-butyl methacrylate; (d) 0% to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2% to 18% by weight of a C12-15 alkyl methacrylate, preferably LMA; (f) 2 wt% to 19.8 wt% of a C16-20 alkyl methacrylate, preferably SMA, and (g) 0% to 1% by weight of styrene monomer and the total amount of component (e) and component (f) is 20% by weight or less.

2. The polyalkyl (meth)acrylate polymer according to claim 1, having a weight average molecular weight in the range of 100,000 g / mol to 1,000,000 g / mol, more preferably in the range of 300,000 g / mol to 900,000 g / mol, and particularly preferably in the range of 500,000 g / mol to 900,000 g / mol.

3. (A) 60 wt. % to 80 wt. % of a base oil, and (B) the following monomers: (a) 6% to 12% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 1% by weight of methyl methacrylate; (c) 45% to 70% by weight of n-butyl methacrylate; (d) 0% to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2% to 18% by weight of a C12-15 alkyl methacrylate, preferably LMA; (f) 2 wt% to 19.8 wt% of a C16-20 alkyl methacrylate, preferably SMA, and (g) 0% to 1% by weight of styrene monomer 20% by weight to 40% by weight of a polyalkyl(meth)acrylate polymer, wherein the total of component (e) and component (f) is 20% by weight or less.

1. An additive composition comprising:

4. 4. The additive composition of claim 3, comprising 70% to 75% by weight of component (A) and 25% to 30% by weight of component (B).

5. (A) 75 to 99.5 wt. % of a base oil; (B) the following monomers: (a) 6% to 12% by weight of an ester of (meth)acrylic acid with hydroxylated hydrogenated polybutadiene; (b) 0% to 1% by weight of methyl methacrylate; (c) 45% to 70% by weight of n-butyl methacrylate; (d) 0% to 20% by weight of a C5-11 alkyl methacrylate; (e) 0.2% to 18% by weight of a C12-15 alkyl methacrylate, preferably LMA; (f) 2 wt% to 19.8 wt% of a C16-20 alkyl methacrylate, preferably SMA, and (g) 0% to 1% by weight of styrene monomer 0.5 to 10% by weight of a polyalkyl(meth)acrylate-based polymer, wherein the total of component (e) and component (f) is 20% by weight or less; and (C) 0 to 15 wt. % of one or more further additives A lubricating oil composition comprising:

6. 6. The lubricating oil composition of claim 5, wherein the one or more further additives (C) are selected from the group consisting of conventional VI improvers, dispersants, antifoam agents, detergents, antioxidants, pour point depressants, antiwear additives, extreme pressure additives, friction modifiers, anticorrosion additives, dyes and mixtures thereof.

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