Poly (meth) alkyl acrylate-based polymers with improved low temperature properties

Abstract

The present invention relates to poly (alkyl (meth) acrylate-based polymers comprising defined amounts of long-chain alkyl (meth) acrylates, their preparation, lubricant compositions comprising such polymers and their use for improving the thickening efficiency and low temperature properties of lubricant compositions, especially engine oil (EO) compositions.

Description

Technical Field

[0001] The present invention relates to polyalkyl (meth)acrylate-based polymers containing a defined amount of long-chain alkyl (meth)acrylate, their preparation, lubricant compositions containing such polymers and their use for improving the thickening efficiency and low temperature properties of lubricant compositions, especially engine oil (EO) compositions. Background Art

[0002] Polyalkyl (meth)acrylate based polymers are well known in the art as highly effective VI improvers.

[0003] US 5,565,130 discloses comb polymers and their use as viscosity index improvers. The working examples contain 10-80% of macromonomers and 20-90% of C1-10 alkyl (meth)acrylates, which exhibit molecular weights Mw in the range of 119,000 to 325,000 g / mol. The effect of the proposed comb polymers on thickening efficiency and low temperature performance is not disclosed.

[0004] WO 2007 / 003238 A1 describes oil-soluble comb polymers based on polyolefin-based macromonomers, in particular polybutadienyl methacrylates and C1-C10 alkyl methacrylates. The working examples contain 37.2-53.3% of macromonomers, 12.3-61% of C1-4 alkyl (meth)acrylates and 12-42.6% of styrene. The weight-average molecular weight Mw of the working examples is in the range of 79,000 to 402,000 g / mol, and D varies from 3.7 to 16.6. The comb polymers can be used as additives for lubricant oils to improve the viscosity index and shear stability. However, the effects of the proposed comb polymers on thickening efficiency and low-temperature performance are not disclosed therein.

[0005] US2010 / 0190671 discloses the use of comb polymers based on polyolefin-based macromonomers, in particular polybutadienyl methacrylate and C1-C10 alkyl methacrylate, for improving the fuel consumption of motor vehicles. The weight average molecular weight Mw of the working examples ranges from 191,000 to 374,000 g / mol, and D varies between 3.5 and 4.5. However, the effect of the proposed comb polymers on low temperature properties is not disclosed therein.

[0006] WO 2018 / 041755 A1 relates to selected comb polymers comprising specified amounts of macromonomers and alkyl acrylates. The presence of 0.5% to 11% by weight of C4-18 alkyl acrylates has a positive effect on the Noack volatility of lubricating compositions comprising such comb polymers. However, the effect of the proposed comb polymers on low temperature properties is not disclosed therein.

[0007] WO 2019 / 012031 relates to comb polymers containing imide functional groups and their use for reducing wear and fuel consumption of engine oil compositions. The effect of the proposed comb polymers on low temperature properties is not disclosed therein.

[0008] EP 3 839 017 A1 relates to polyalkyl (alkyl)acrylate comb polymers which contain at least 21% by weight of C12-24 alkyl (alkyl)acrylate monomers. However, the effect of the proposed comb polymers on low temperature properties is not disclosed therein.

[0009] Lubricating oils need to have a sufficiently high viscosity at operating temperatures to prevent damage to machinery or equipment. Since the viscosity of a liquid depends greatly on temperature, special attention is paid to ensuring a minimum viscosity at maximum high temperatures. These viscosities are usually specified, for example, as a minimum kinematic viscosity at 100°C (KV100) and / or a minimum high temperature high shear viscosity at 150°C (HTHS150).

[0010] Although it is theoretically possible in most cases to adjust lubricant viscosity to the minimum required at high temperatures by simply blending lighter and heavier base oils, the resulting lubricant will not ensure safe and good operation of the equipment under cold start conditions.

[0011] Mineral base oils contain a certain amount of paraffinic species, which tend to form wax crystals and precipitate at low temperatures. Heavier base oils contain more wax than lighter oils, and high amounts of waxy base oil components result in poor low temperature fluidity.

[0012] Pour point depressants (PPDs) are used to partially mitigate the negative effects caused by paraffin crystallization, but their use alone is usually insufficient to meet viscosity requirements at low and high temperatures. Therefore, the viscosity of lubricants is often adjusted by adding viscosity index improvers (VII), also called viscosity modifiers (VM).

[0013] Lighter base oils with sufficient low temperature fluidity are thickened with VM to the desired high temperature values. At high temperatures, the polymer molecules unfold and their hydrodynamic volume increases, resulting in a greater thickening effect. At lower temperatures, the same polymer chains curl up, resulting in a smaller thickening effect. This minimizes parasitic energy losses caused by the lubricant and, for example, makes engines more efficient with lower fuel consumption.

[0014] At high temperatures, the lubricant has a corresponding viscosity and forms a thicker oil film, thereby providing better lubricity (= lower friction) and good wear protection. However, it is necessary to be very careful in selecting a suitable VM, because it should have sufficient shear stability to withstand mechanical stress. Otherwise, this will lead to an undesirable loss of viscosity and, again, to a too low viscosity of the lubricant. In addition to other additives in the lubricant, the combined use of light base oils, heavier base oils, one or more PPDs and VMs is well known to those skilled in the art. It is also a well-known and recognized fact that an increase in the number of additives and components will increase the cost of the resulting lubricant. Not only is the simple component cost of the individual additives added up, but it also leads to a high degree of complexity in the operation of blending these lubricants, thereby further increasing costs. Therefore, every lubricant formulator seeks to maximize the use of heavier base oils while minimizing the use of other additives. Summary of the invention

[0015] One object of the present invention is to combine the properties of a viscosity improver with those of a pour point depressant in one molecule while maintaining all the desirable properties of a viscosity improver, such as VI boosting properties (for both high and low shear viscosity measurement performance), shear stability and good low temperature performance. The goal is to formulate a high grade multi-purpose lubricant that meets a set of demanding gear and engine oil viscosity specifications with a range of mineral base oils and viscosity modifiers without the additional need for one or more PPDs.

[0016] It has now surprisingly been found that polyalkyl (meth)acrylate-based polymers comprising a certain amount of long-chain alkyl (meth)acrylates lead to improved low temperature properties of lubricant compositions, especially engine oil (EO) compositions. DETAILED DESCRIPTION OF THE INVENTION

[0018] The first object of the present invention relates to a polyalkyl (meth)acrylate-based polymer comprising the following monomers:

[0019] (a) 5 to 15% by weight of an ester of (meth)acrylic acid and hydroxylated hydrogenated polybutadiene;

[0020] (b) 0 to 2% by weight of methyl methacrylate;

[0021] (c) 45% to 80% by weight of n-butyl methacrylate;

[0022] (d) 0 to 20% by weight of C5-11 alkyl methacrylate, preferably isodecyl methacrylate;

[0023] (e) 0.2 to 18% by weight of C12-15 alkyl methacrylate, preferably C12-14 alkyl methacrylate;

[0024] (f) 2 to 19.8 wt% of C16-20 alkyl methacrylate, preferably octadecyl methacrylate; and

[0025] (g) 0 to 2% by weight of styrene monomer,

[0026] The sum of components (e) and (f) is equal to or less than 20% by weight.

[0027] The content of each component (a), (b), (c), (d), (e), (f) and (g) is based on the total composition of the polyalkyl (meth)acrylate-based polymer.

[0028] In a particular embodiment, the proportions of components (a), (b), (c), (d), (e), (f) and (g) add up to 100% by weight.

[0029] A further object of the present invention relates to a polyalkyl (meth)acrylate based polymer comprising the following monomers:

[0030] (a) 6 to 12% by weight of an ester of (meth)acrylic acid and hydroxylated hydrogenated polybutadiene;

[0031] (b) 0 to 1% by weight of methyl methacrylate;

[0032] (c) 45 to 70% by weight of n-butyl methacrylate;

[0033] (d) 0 to 20% by weight of C5-11 alkyl methacrylate;

[0034] (e) 0.2 to 18 wt% of C12-15 alkyl methacrylate, preferably LMA;

[0035] (f) 2 to 19.8 wt% of C16-20 alkyl methacrylate, preferably SMA; and

[0036] (g) 0 to 1% by weight of styrene monomer,

[0037] The sum of components (e) and (f) is equal to or less than 20% by weight.

[0038] A further object of the present invention relates to a polyalkyl (meth)acrylate based polymer consisting of the following monomers:

[0039] (a) 9 to 12% by weight of an ester of (meth)acrylic acid and hydroxylated hydrogenated polybutadiene;

[0040] (b) 0 to 1% by weight of methyl methacrylate;

[0041] (c) 60 to 70% by weight of n-butyl methacrylate;

[0042] (d) 0 to 20% by weight of C5-11 alkyl methacrylate;

[0043] (e) 0.2 to 18% by weight of C12-15 alkyl methacrylate;

[0044] (f) 2 to 19.8 wt% of C16-20 alkyl methacrylate; and

[0045] (g) 0 to 1% by weight of styrene monomer,

[0046] The sum of components (e) and (f) is equal to or less than 20% by weight.

[0047] The content of each component (a), (b), (c), (d), (e) and (f) is based on the total composition of the polyalkyl (meth)acrylate-based polymer.

[0048] In a particular embodiment, the proportions of components (a), (b), (c), (d), (e) and (f) add up to 100% by weight.

[0049] The weight average molecular weight of the polyalkyl (meth)acrylate-based polymer according to the present invention is preferably 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, particularly preferably in the range of 500,000 g / mol to 900,000 g / mol, and the number average molecular weight of the polyalkyl (meth)acrylate-based comb polymer according to the present invention is preferably in the range of 100,000 g / mol to 300,000 g / mol, more preferably in the range of 100,000 g / mol to 200,000 g / mol, particularly preferably in the range of 110,000 g / mol to 160,000 g / mol.

[0050] In the present invention, the polyalkyl (meth) acrylate polymer comprises a first polymer (also referred to as a backbone or main chain) and a plurality of additional polymers (referred to as side chains and covalently bonded to the main chain). In this case, the main chain of the polyalkyl (meth) acrylate polymer is formed by interconnected unsaturated groups of the mentioned (meth) acrylate. The ester groups of the (meth) acrylate, the phenyl residues of the styrene monomers and the substituents of the additional free radical polymerizable comonomers form the side chains of the polyalkyl (meth) acrylate polymer.

[0051] The term "methacrylate" refers to esters of methacrylic acid; the term "(meth)acrylate" refers to both esters of acrylic acid and esters of methacrylic acid.

[0052] The hydroxylated hydrogenated polybutadienes used according to the invention have a number-average molar mass 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 in the present invention as macroalcohols.

[0053] 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 with THF as eluent.

[0054] 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 copolymers of the present invention is the iodine value. The iodine value refers to the grams of iodine that can be added to 100 grams of copolymer. Preferably, the copolymers of the present invention have an iodine value of no more than 5 grams of iodine / 100 grams of copolymer. The iodine value is determined by the Wijs method according to DIN 53241-1:1995-05.

[0055] Preferred hydroxylated hydrogenated polybutadienes are obtainable according to GB 2270317.

[0056] Some hydroxylated hydrogenated polybutadienes are also commercially available. Commercially available hydroxylated hydrogenated polybutadienes include, for example, hydrogenated polybutadiene functionalized to a degree of about 98% by weight (also known as olefin copolymer OCP) from Cray Valley (Paris), a subsidiary of Total (Paris), which has about 50% each of 1,2 repeat units and 1,4 repeat units, Mn = 4200 g / mol.

[0057] Preferred is monohydroxylated hydrogenated polybutadiene. More preferably, the hydroxylated hydrogenated polybutadiene is hydroxyethyl- or hydroxypropyl-terminated hydrogenated polybutadiene. Particularly preferred is hydroxypropyl-terminated polybutadiene.

[0058] These monohydroxylated hydrogenated polybutadienes can be prepared by first converting butadiene monomers into polybutadiene via anionic polymerization. Subsequently, hydroxyl-functionalized polybutadiene can be prepared by reacting the polybutadiene monomers with ethylene oxide or propylene oxide. Such hydroxylated polybutadiene can be hydrogenated in the presence of a suitable transition metal catalyst.

[0059] Owing to their high molar mass, the esters of (meth)acrylic acid and of the hydroxylated hydrogenated polybutadienes used according to the invention are also referred to in the present invention as macromonomers.

[0060] The macromonomers used according to the invention can be prepared by transesterification of alkyl (meth)acrylates. The reaction of alkyl (meth)acrylates with hydroxylated hydrogenated polybutadiene forms the esters according to the invention. Methyl (meth)acrylate or ethyl (meth)acrylate is preferably used as reactant.

[0061] Such transesterification is well known. For example, it is possible to use heterogeneous catalyst systems, such as lithium hydroxide / calcium oxide mixtures (LiOH / CaO), pure lithium hydroxide (LiOH), lithium methoxide (LiOMe) or sodium methoxide (NaOMe), or homogeneous catalyst systems, such as isopropyl titanate (Ti(OiPr) 4) or dioctyltin oxide (Sn(OCt) 2 O). The reaction is an equilibrium reaction. Therefore, the released low molecular weight alcohol is usually removed, for example, by distillation.

[0062] Furthermore, the macromonomers can be obtained, for example, by direct esterification starting from (meth)acrylic acid or (meth)acrylic anhydride, preferably under acidic catalysis with p-toluenesulfonic acid or methanesulfonic acid, or from free methacrylic acid by the DCC process (dicyclohexylcarbodiimide).

[0063] Furthermore, the hydroxylated hydrogenated polybutadiene of the present invention can be converted into an ester by reacting with an acid chloride, such as (meth)acryloyl chloride.

[0064] Preferably, in the above-detailed preparation of the esters of the invention, a polymerization inhibitor is used, for example 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy free radical and / or hydroquinone monomethyl ether.

[0065] The C5-11 alkyl (meth)acrylate used according to the present invention is an ester of acrylic acid or methacrylic acid with an alcohol having 5 to 11 carbon atoms. The term "C5-11 alkyl (meth)acrylate" includes a single acrylic acid or methacrylic acid ester of an alcohol of a specific length, and also includes a mixture of methacrylic acid esters of alcohols of different lengths.

[0066] 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.

[0067] A particularly preferred C5-11 alkyl (meth)acrylate is isodecyl methacrylate.

[0068] The C12-15 alkyl (meth)acrylate used according to the present invention is an ester of acrylic acid or methacrylic acid with an alcohol having 12 to 15 carbon atoms. The term "C12-15 alkyl (meth)acrylate" includes a single acrylic acid or methacrylic acid ester of an alcohol of a specific length, and also includes a mixture of methacrylic acid esters of alcohols of different lengths.

[0069] 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.

[0070] Particularly preferred C11-15 alkyl (meth)acrylates are methacrylates of mixtures of linear C12-14 alcohols; most preferred are C12-14 alkyl methacrylates.

[0071] The C16-20 alkyl (meth)acrylate used according to the present invention is an ester of (meth)acrylic acid and a linear or branched alcohol having 16 to 20 carbon atoms. The term "C16-20 alkyl (meth)acrylate" includes a single (meth)acrylate of an alcohol of a specific length, and also includes a mixture of (meth)acrylates of alcohols of different lengths.

[0072] 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.

[0073] The polyalkyl(meth)acrylate-based polymers according to the invention can be prepared by free-radical polymerization and by related processes of controlled radical polymerization, such as ATRP (=atom transfer radical polymerization) or RAFT (=reversible addition fragmentation chain transfer).

[0074] Standard free-radical polymerization is described in detail in particular in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition. Typically, polymerization initiators and optionally chain transfer agents are used for this purpose.

[0075] Useful initiators include azo initiators well known in the art, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, and peroxide compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauroyl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5- Dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, diisopropylbenzene peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, cumene hydroperoxide, tert-butyl hydroperoxide, bis(4-tert-butylcyclohexyl)peroxydicarbonate, mixtures of two or more of the above compounds with one another, and mixtures of the above compounds with unspecified compounds which likewise form free radicals. Suitable chain transfer agents are, in particular, oil-soluble mercaptans, for example n-dodecyl mercaptan or 2-mercaptoethanol, or chain transfer agents from the class of terpenes, for example terpinolene.

[0076] The ATRP method itself is known. It is presumed that this is a "living" free radical polymerization, but there is no intention to limit the description of this mechanism. In these methods, a transition metal compound is reacted with a compound having a transferable atomic group. This involves transferring the transferable atomic group to the transition metal compound, which is then oxidized. This reaction forms a free radical, which is added to the olefinic group. However, it is reversible for the atomic group to be transferred to the transition metal compound, so that the atomic group is transferred back to the growing polymer chain, which results in the formation of a controlled polymerization system. The formation, molecular weight and molecular weight distribution of the polymer can be controlled accordingly.

[0077] Such as JS.Wang et al., J.Am.Chem.Soc., Vol. 117, pp. 5614-5615 (1995), Matyjaszewski, Macromolecules, Vol. 28, pp. 7901-7910 (1995) describe this reaction mechanism. In addition, patent applications WO 96 / 30421, WO 97 / 47661, WO 97 / 18247, WO 98 / 40415 and WO 99 / 10387 disclose variants of the above-mentioned ATRP. In addition, the polymer of the present invention can also be obtained by, for example, the RAFT method. Such a method is described in detail in, for example, WO 98 / 01478 and WO 2004 / 083169.

[0078] The polymerization can be carried out under standard pressure, reduced pressure or elevated pressure. The polymerization temperature is also not critical. However, generally, it is in the range of -20°C to 200°C, preferably 50°C to 150°C, more preferably 80°C to 130°C.

[0079] The polymerization can be carried out with or without solvent. The term "solvent" should be understood in a broad sense. The solvent is selected according to the polarity of the monomers used, preferably 100N oil, relatively light gas oil and / or aromatic hydrocarbons, such as toluene or xylene, can be used.

[0080] 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.

[0081] A second object of the present invention relates to an additive composition comprising:

[0082] (A) 60% to 80% by weight of a base oil, and

[0083] (B) 20 to 40 wt% of a polyalkyl (meth)acrylate-based polymer comprising the following monomers:

[0084] (a) 5 to 15% by weight of an ester of (meth)acrylic acid and hydroxylated hydrogenated polybutadiene;

[0085] (b) 0 to 2% by weight of methyl methacrylate;

[0086] (c) 45% to 80% by weight of n-butyl methacrylate;

[0087] (d) 0 to 20% by weight of C5-11 alkyl methacrylate;

[0088] (e) 0.2 to 18% by weight of C12-15 alkyl methacrylate;

[0089] (f) 2% to 19.8% by weight of C16-20 alkyl methacrylate; and

[0090] (g) 0 to 2% by weight of styrene monomer,

[0091] The sum of components (e) and (f) is equal to or less than 20% by weight.

[0092] A further second object of the present invention relates to an additive composition comprising:

[0093] (A) 60% to 80% by weight of a base oil, and

[0094] (B) 20 to 40 wt% of a polyalkyl (meth)acrylate-based polymer comprising the following monomers:

[0095] (a) 6 to 12% by weight of an ester of (meth)acrylic acid and hydroxylated hydrogenated polybutadiene;

[0096] (b) 0 to 1% by weight of methyl methacrylate;

[0097] (c) 45 to 70% by weight of n-butyl methacrylate;

[0098] (d) 0 to 20% by weight of C5-11 alkyl methacrylate;

[0099] (e) 0.2 to 18 wt% of C12-15 alkyl methacrylate, preferably LMA;

[0100] (f) 2 to 19.8 wt% of C16-20 alkyl methacrylate, preferably SMA; and

[0101] (g) 0 to 1% by weight of styrene monomer,

[0102] The sum of components (e) and (f) is equal to or less than 20% by weight.

[0103] A further second object of the present invention relates to an additive composition comprising:

[0104] (A) 60% to 80% by weight of a base oil, and

[0105] (B) 20 to 40 wt% of a polyalkyl (meth)acrylate-based polymer consisting of the following monomers:

[0106] (a) 9 to 12% by weight of an ester of (meth)acrylic acid and hydroxylated hydrogenated polybutadiene;

[0107] (b) 0 to 1% by weight of methyl methacrylate;

[0108] (c) 60 to 70% by weight of n-butyl methacrylate;

[0109] (d) 0 to 20% by weight of C5-11 alkyl methacrylate;

[0110] (e) 0.2 to 18% by weight of C12-15 alkyl methacrylate;

[0111] (f) 2% to 19.8% by weight of C16-20 alkyl methacrylate; and

[0112] (g) 0 to 1% by weight of styrene monomer.

[0113] The sum of components (e) and (f) is equal to or less than 20% by weight.

[0114] The content of each of components (A) and (B) is based on the total composition of the additive composition.

[0115] In a particular embodiment, the proportions of components (A) and (B) add up to 100% by weight.

[0116] The content of each component (a), (b), (c), (d), (e), (f) and (g) is based on the total composition of the polyalkyl (meth)acrylate-based polymer.

[0117] In a particular embodiment, the proportions of components (a), (b), (c), (d), (e), (f) and (g) add up to 100% by weight.

[0118] The base oil to be used in the additive composition comprises an oil of lubricating viscosity. Such oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.

[0119] 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 edition, Section 1.3, Subtitle 1.3. "Base Stock Categories").

[0120] API currently defines five classes of lubricant base stocks (API 1509, Appendix E - API Base Stock Interchangeability Guidelines for Passenger Car Engine Oils and Diesel Engine Oils, September 2011). Classes I, II and III are mineral oils classified by the amount of saturates and sulfur they contain and by their viscosity index; Class IV are polyalphaolefins; Class V are all other base stocks, including, for example, ester oils. The ester oils that can be used according to the invention are preferably selected from Plastomoll DNA, DIOS and mixtures thereof; DIOS is more preferred. The following table shows these API classifications.

[0121]

[0122] The kinematic viscosity (KV) at 100° C. of a suitable nonpolar base oil for preparing the additive composition or lubricating composition according to the present invention is as follows: 100 ) preferably at 3mm 2 / s to 10mm 2 / s, more preferably within 4mm 2 / s to 8mm 2 / s range.

[0123] Further base oils which may be used according to the present invention are Group II-III Fischer-Tropsch derived base oils.

[0124] 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 a Fischer-Tropsch process. Fischer-Tropsch derived base oils may also be referred to as GTL (gas to liquid) base oils. Suitable Fischer-Tropsch derived base oils that may be conveniently used as base oils in the lubricating compositions of the present invention are those disclosed in, for example, EP 0 776 959, EP 0 668342, 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.

[0125] Especially for 0W and 5W engine oil formulations, API Group III oils are often used.

[0126] The additive composition of the present invention preferably comprises 70 to 75 wt % of a base oil (component (A)) and 25 to 30 wt % of a polyalkyl (meth)acrylate-based polymer (component (B)), based on the total weight of the additive composition.

[0127] The third object of the present invention relates to a lubricating oil composition comprising:

[0128] (A) 75% to 99.5% by weight of a base oil;

[0129] (B) 0.5 to 10 wt% of a polyalkyl (meth)acrylate-based polymer comprising the following monomers:

[0130] (a) 5 to 15% by weight of an ester of (meth)acrylic acid and hydroxylated hydrogenated polybutadiene;

[0131] (b) 0 to 2% by weight of methyl methacrylate;

[0132] (c) 45% to 80% by weight of n-butyl methacrylate;

[0133] (d) 0 to 20% by weight of C5-11 alkyl methacrylate;

[0134] (e) 0.2 to 18% by weight of C12-15 alkyl methacrylate;

[0135] (f) 2% to 19.8% by weight of C16-20 alkyl methacrylate; and

[0136] (g) 0 to 2% by weight of styrene monomer,

[0137] wherein the sum of components (e) and (f) is equal to or less than 20 wt %; and

[0138] (C) 0% to 15% by weight of one or more additional additives.

[0139] A further third object of the present invention relates to a lubricating oil composition comprising:

[0140] (A) 75% to 99.5% by weight of a base oil;

[0141] (B) 0.5 to 10 wt% of a polyalkyl (meth)acrylate-based polymer comprising the following monomers:

[0142] (a) 6 to 12% by weight of an ester of (meth)acrylic acid and hydroxylated hydrogenated polybutadiene;

[0143] (b) 0 to 1% by weight of methyl methacrylate;

[0144] (c) 45 to 70% by weight of n-butyl methacrylate;

[0145] (d) 0 to 20% by weight of C5-11 alkyl methacrylate;

[0146] (e) 0.2 to 18% by weight of C12-15 alkyl methacrylate;

[0147] (f) 2 to 19.8 wt% of C16-20 alkyl methacrylate; and

[0148] (g) 0 to 1% by weight of styrene monomer,

[0149] wherein the sum of components (e) and (f) is equal to or less than 20 wt %; and

[0150] (C) 0% to 15% by weight of one or more additional additives.

[0151] A further third object of the present invention relates to a lubricating oil composition comprising:

[0152] (A) 75% to 99.5% by weight of a base oil;

[0153] (B) 0.5 to 10 wt% of a polyalkyl (meth)acrylate-based polymer consisting of the following monomers:

[0154] (a) 9 to 12% by weight of an ester of (meth)acrylic acid and hydroxylated hydrogenated polybutadiene;

[0155] (b) 0 to 1% by weight of methyl methacrylate;

[0156] (c) 60 to 70% by weight of n-butyl methacrylate;

[0157] (d) 0 to 20% by weight of C5-11 alkyl methacrylate;

[0158] (e) 0.2 to 18% by weight of C12-15 alkyl methacrylate;

[0159] (f) 2 to 19.8 wt% of C16-20 alkyl methacrylate; and

[0160] (g) 0 to 1% by weight of styrene monomer,

[0161] wherein the sum of components (e) and (f) is equal to or less than 20 wt %; and

[0162] (C) 0% to 15% by weight of one or more additional additives.

[0163] The content of each of components (A), (B) and (C) is based on the total composition of the lubricating oil composition.

[0164] The content of each component (a), (b), (c), (d), (e), (f) and (g) is based on the total composition of the polyalkyl (meth)acrylate-based polymer.

[0165] In a particular embodiment, the proportions of components (a), (b), (c), (d), (e), (f) and (g) add up to 100% by weight.

[0166] The lubricating oil composition according to the present invention may also contain as component (C) additional additives selected from the group consisting of conventional VI improvers, dispersants, defoamers, detergents, antioxidants, pour point depressants, antiwear additives, extreme pressure additives, friction modifiers, anticorrosion additives, dyes and mixtures thereof.

[0167] Conventional VI improvers include hydrogenated styrene-diene copolymers (HSD, US Pat. No. 4,116,917, US Pat. No. 3,772,196 and US Pat. No. 4,788,316), in particular based on butadiene and isoprene, and olefin copolymers (OCP, K. Marsden: "Literature Review of OCP Viscosity Modifiers", Lubrication Science 1 (1988), 265), in particular of the poly(ethylene-co-propylene) type, which can often also be present in N / O-functional form with dispersant action, or PAMA, which is usually present in N-functional form with advantageous additive properties (promoter) as dispersant, wear protection additive and / or friction modifier ( and DE 1520 696 of Haas, WO 2006 / 007934 of RohMax Additives).

[0168] Compilations of VI improvers and pour point improvers for lubricant oils, especially engine oils, are described in detail, for example, in T. Mang, W. Dresel (eds.): "Lubricants and Lubrication", Wiley-VCH, Weinheim 2001; RM Mortier, ST Orszulik (eds.): "Chemistry and Technology of Lubricants", Blackie Academic & Professional, London 1992; or J. Bartz: "Additive für Schmierstoffe", Expert Publishers, Renningen-Malmsheim 1994.

[0169] Suitable dispersants include poly(isobutylene) derivatives, such as poly(isobutylene) succinimide (PIBSI), including boronated PIBSI; and ethylene-propylene oligomers having N / O functional groups.

[0170] Dispersants (including boronated dispersants) are preferably used in an amount of 0 to 5 wt %, based on the total amount of the lubricating oil composition.

[0171] Suitable defoaming agents are silicone oil, fluorosilicone oil, fluoroalkyl ether and the like.

[0172] The defoaming 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.

[0173] Preferred detergents include metal-containing compounds, such as phenoxides; salicylates; thiophosphonates, especially thiopyrophosphonates, thiophosphonates and phosphonates; sulfonates and carbonates. As metals, these compounds may contain, inter alia, calcium, magnesium and barium. These compounds may preferably be used in neutral or overbased form.

[0174] The detergent is preferably used in an amount of 0.2 to 1 wt % based on the total amount of the lubricating oil composition.

[0175] Suitable antioxidants include, for example, phenol-based antioxidants and amine-based antioxidants.

[0176] Phenol-based antioxidants include, for example, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 4,4'-bis(2-methyl-6-tert-butylphenol); 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); tert-butylphenol); 4,4'-butylenebis(3-methyl-6-tert-butylphenol); 4,4'-isopropylidenebis(2,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-tert-butyl-4-methylphenol; 2 ,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; 2,6-di-tert-amyl-p-cresol; 2,6-di-tert-butyl-4-(N,N'-dimethylaminomethylphenol); 4,4'-thiobis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(3-methyl-6-tert-butylphenol); 2,2'-thiobis(4-methyl-6-tert-butylphenol ); bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide; 3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate n-octyl ester; 3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate n-octadecyl ester; 2,2'-thio[diethyl-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], etc. Among them, bisphenol-based antioxidants and phenol-based antioxidants containing ester groups are particularly preferred.

[0177] Amine-based antioxidants include, for example, monoalkyldiphenylamines, such as monooctyldiphenylamine, monononyldiphenylamine, etc.; dialkyldiphenylamines, such as 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, etc.; polyalkyldiphenylamines, such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine, etc.; naphthylamines, specifically α-naphthylamine, phenyl-α-naphthylamine and other alkyl-substituted phenyl-α-naphthylamines, such as butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine, nonylphenyl-α-naphthylamine, etc. Among them, diphenylamine is preferred over naphthylamine from the viewpoint of its antioxidant effect.

[0178] Suitable antioxidants may further be selected from compounds containing sulfur and phosphorus, for example metal dithiophosphates, such as zinc dithiophosphate (ZnDTP), "OOS triesters" = reaction products of dithiophosphoric acids with activated double bonds from olefins, cyclopentadiene, norbornadiene, α-pinene, polybutene, acrylates, maleates (ashless when burned); organic sulfur compounds, such as dialkyl sulfides, diaryl sulfides, polysulfides, modified mercaptans, thiophene derivatives, xanthates, thioglycols, thioaldehydes, sulfur-containing carboxylic acids; heterocyclic sulfur / nitrogen compounds, especially dialkyldimercaptothiadiazoles, 2-mercaptobenzimidazoles; zinc bis(dialkyldithiocarbamates) and methylenebis(dialkyldithiocarbamates); organic phosphorus compounds, such as triaryl and trialkyl phosphites; organic copper compounds and overbased calcium- and magnesium-based phenoxides and salicylates.

[0179] The antioxidant is used in an amount of 0 to 15 wt %, preferably 0.1 to 10 wt %, more preferably 0.5 to 5 wt %, based on the total amount of the lubricating oil composition.

[0180] Pour point depressants include ethylene-vinyl acetate copolymers, chlorinated paraffin-naphthalene condensates, chlorinated paraffin-phenol condensates, polymethacrylates, polyalkylstyrenes, etc. Preferred are polymethacrylates having a mass average molecular weight of 5,000 to 50,000 g / mol.

[0181] The amount of the pour point depressant is preferably 0.1 to 5 wt %, based on the total amount of the lubricating oil composition.

[0182] Preferred antiwear and extreme pressure additives include sulfur-containing compounds such as zinc dithiophosphate, di-C 3-12 - Zinc alkyl dithiophosphates (ZnDTP), zinc phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, disulfides, sulfurized olefins, sulfurized oils and fats, 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 monoalkyl and dialkyl phosphates, ethoxylated monoalkyl 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.

[0183] 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.

[0184] The friction modifiers used may include mechanically active compounds such as molybdenum disulfide, graphite (including graphite fluoride), poly(trifluoroethylene), polyamide, polyimide; 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 reactions, such as saturated fatty acids, phosphoric acid and thiophosphates, xanthates, sulphurized fatty acids; compounds that form polymer-like layers, such as ethoxylated dicarboxylic acid partial esters, dialkyl phthalates, methacrylates, unsaturated fatty acids, sulphurized olefins or organometallic compounds, such as molybdenum compounds (molybdenum dithiophosphates and molybdenum dithiocarbamates MoDTC) and their combinations with ZnDTP, copper-containing organic compounds.

[0185] The friction modifier may be used in an amount of 0 to 6 wt %, preferably 0.05 to 4 wt %, more preferably 0.1 to 2 wt %, based on the total amount of the lubricating oil composition.

[0186] Some of the compounds listed above may fulfill multiple functions. For example, ZnDTP is primarily an anti-wear additive and an extreme pressure additive, but also has the characteristics of an antioxidant and a corrosion inhibitor (here: a metal passivator / deactivator).

[0187] The additives specified above are described in detail in particular in T. Mang, W. Dresel (eds.): "Lubricants and Lubrication", Wiley-VCH, Weinheim 2001; RM Mortier, ST Orszulik (eds.): "Chemistry and Technology of Lubricants".

[0188] Preferably, the total concentration of the one or more additives (C) is from 0.05 to 15 wt%, more preferably from 3 to 10 wt%, based on the total weight of the lubricating oil composition.

[0189] The invention is illustrated by the following non-limiting examples. DETAILED DESCRIPTION

[0190] Experimental Section

[0191] abbreviation

[0192] AMA Alkyl Methacrylate

[0193] Group II / III oil KV100 is 1 cSt light process oil

[0194] BMA n-butyl methacrylate

[0195] C1 AMA C1-alkyl methacrylate = methyl methacrylate (MMA)

[0196] C4 AMA C4-alkyl methacrylate = n-butyl methacrylate (BMA)

[0197] C12-15 AMA Mixture of C12-15-alkyl methacrylates

[0198] C16-18 AA A mixture of C16-18 alkyl acrylates

[0199] 100N oil KV100 is 4cSt Group II base oil

[0200] DDM Dodecanethiol

[0201] HTHS80 High temperature high shear viscosity @80°C, measured according to CEC L-036

[0202] HTHS100 High temperature high shear viscosity @100°C, measured according to CEC L-036

[0203] HTHS150 High temperature high shear viscosity @150°C, measured according to CEC L-036

[0204] IDMA Isodecyl methacrylate containing up to 15% by weight of C11 alkyl methacrylate

[0205] KV Kinematic viscosity measured according to ASTM D445

[0206] KV40 Kinematic viscosity @40°C, measured according to ISO 3104

[0207] KV100 Kinematic viscosity @100°C, measured according to ISO 3104

[0208] LMA Lauryl Methacrylate, 73% C12, 27% C14, all linear

[0209] MM Macromonomer

[0210] MMA Methyl Methacrylate

[0211] M n Number average molecular weight

[0212] M w Weight average molecular weight

[0213] NB 3020 3020, Group III base oil from Neste, KV100 is 2.2 cSt

[0214] NB 3043 3043, Group III base oil from Neste, KV100 is 4.3 cSt

[0215] OLOA 9728X DI package for PCMO, available from Oronite

[0216] PCMO Passenger Car Engine Oil

[0217] PDI Polydispersity Index

[0218] SMA C16-20 alkyl methacrylate, all linear

[0219] VI Viscosity Index, measured according to ISO 2909

[0220] Test methods

[0221] The molecular weight and PDI of the polyalkyl (meth)acrylate based polymers according to the present invention and comparative examples were characterized.

[0222] Molecular weights were determined by size exclusion chromatography (SEC) using commercially available polymethyl methacrylate (PMMA) standards. Determinations were performed by gel permeation chromatography using THF as eluent (flow rate: 1 mL / min; injection volume: 100 μl).

[0223] Columns: 5 SDV columns 8×300 mm or 8×50 mm (Company PSS in Mainz)

[0224] 1 solvent peak separation column 8×100 mm (Shodex)

[0225]

[0226] Instrument: Agilent 1100 Series Pump G1310A

[0227] PSS SECurity Online Degasser 409-0024

[0228] Agilent 1260 Series Autosampler G1329B

[0229] Agilent 1260 Series UV Detector G1314B

[0230] Agilent 1100 Series RI Detector G1362A

[0231] Agilent 1100 Series Control Module G1323B

[0232] Techlab Column Oven K-5

[0233] Oven: Temperature 35℃

[0234] Eluent: Tetrahydrofuran

[0235] The eluent is continuously distilled and circulated through a pump

[0236] Flow rate: 1ml / min

[0237] Injection volume: 100 μl

[0238] Detection: RI: Temperature 35℃

[0239] UV: Wavelength 239nm

[0240] Delay volume: 0.175 ml (between UV signal and RI signal)

[0241] Software:PSS WinGPC-Software

[0242] Sample solution concentration: 2g / L (Mw>106: 1g / L...0.5g / L)

[0243] Standard sample: PMMA (such as PSS (Mainz) or Polymer Laboratories)

[0244] Standard solution concentration: 1 g / l (for Mw>106: 0.5 g / l, Mw>2*106: 0.25 g / l) (narrow distribution)

[0245] Internal standard: 1,2-dichlorobenzene → 0.2μL to 99.8μL sample

[0246] The lubricating oil compositions comprising 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 D 2270 and pour point according to ASTM D-5950.

[0247] They were further characterized for their Brookfield viscosity at -40°C according to DIN 51398, CCS (Cold Crank Simulator) apparent viscosity at -30°C according to ASTM D 5293 and yield stress at -35°C according to ASTM D-4684 (Micro Rotational Viscometer - MRV-TP1).

[0248] To indicate the shear stability of a lubricating oil composition, the PSSI (Permanent Shear Stability Index) was calculated according to ASTM D 6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index) based on data measured according to ASTM D-445 / CEC L-45-A-99 ("Kegelrollenlager (Tapered Roller Bearing)" - KRL, 20 hours at 60°C, 5 kN, 1475 + / - 25 rpm).

[0249] 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 D 6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index).

[0250] Synthesis of Hydroxylated Hydrogenated Polybutadiene

[0251] The prepared macromolecular alcohol has an average molar mass M n = 4750 g / mol of hydroxypropyl terminated hydrogenated polybutadiene.

[0252] The macroalcohol is synthesized by anionic polymerization of 1,3-butadiene with butyl lithium at 20-45°C. After reaching the desired degree of polymerization, the reaction is terminated by addition of propylene oxide and the lithium is removed by precipitation with methanol. Subsequently, the polymer is hydrogenated in a hydrogen atmosphere in the presence of a noble metal catalyst at up to 140°C and a pressure of 200 bar. After the hydrogenation is complete, the noble metal catalyst is removed and the organic solvent is pumped off under reduced pressure. Finally, the base oil NB 3020 is used for dilution to a polymer content of 70% by weight.

[0253] The macroalcohol has a vinyl content of 61%, a hydrogenation level of >99% and an OH functionality of >98%. These values ​​were determined by 1H-NMR (nuclear magnetic resonance spectroscopy).

[0254] Synthesis of macromonomer (MM)

[0255] In a 2-liter stirring apparatus equipped with a saber stirrer, a gas inlet, a thermocouple with a controller, a heating mantle, a column with a 3 mm wire spiral random packing, a vapor distributor, a top thermometer, a reflux condenser and a base cooler, 1000 g of the above macroalcohol was dissolved in 450 g of methyl methacrylate (MMA) by stirring at 60° C. To this solution were added 20 ppm of 2,2,6,6-tetramethylpiperidin-1-oxyl free radical and 200 ppm of hydroquinone monomethyl ether. After heating to MMA reflux (bottom temperature about 110° C.) while passing air through for stabilization, about 20 g of MMA were distilled off for azeotropic drying. After cooling to 95° C., 0.30 g of LiOCH3 were added and the mixture was heated back to reflux. After a reaction time of about 1 hour, the top temperature dropped to ~64° C. due to the formation of methanol. The methanol / MMA azeotrope formed was continuously distilled off until a constant top temperature of about 100° C. was established again. At this temperature, the mixture was allowed to react for a further hour. For further work-up, most of the MMA was drawn off under reduced pressure. Insoluble catalyst residues were removed by filter pressing (Seitz T1000 depth filter). The content of NB 3020 "carried over" into the copolymer synthesis described further below was taken into account accordingly.

[0256] Synthesis of Example 1

[0257] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.16 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.27 g t-butyl peroxy-2-ethylhexanoate and 2.45 g NB3043 was added over a period of 240 minutes.

[0258] 240 minutes after the start of the reaction, an additional 87.5 grams of NB3043 were added over a period of 120 minutes. At the same time, a mixture of 0.35 grams of t-butyl peroxy-2-ethylhexanoate and 3.15 grams of NB3043 were added over a period of 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 grams of LMA and 2.57 grams of SMA was added to the heel to help reduce BMA residues.

[0259] The mixture was stirred overnight at 90° C. The next day, 256.90 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0260] Synthesis of Example 2

[0261] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90° C. Thereafter, 1.16 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting of 0.10 g of MM (70% in NB 3020), 15.80 g of SMA, 0.20 g of styrene, 61.20 g of BMA, 0.60 g of MMA, 57.00 g of NB3043 and 20.80 g of Group II / III oil was added over a period of 180 minutes. Simultaneously, a second mixture of 0.27 g of t-butyl peroxy-2-ethylhexanoate and 2.45 g of NB3043 was added over a period of 240 minutes.

[0262] 240 minutes after the start of the reaction, an additional 87.50 grams of NB3043 were added over a period of 120 minutes. At the same time, a mixture of 0.35 grams of t-butyl peroxy-2-ethylhexanoate and 3.15 grams of NB3043 were added over a period of 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 grams of LMA and 2.60 grams of SMA were added to the tail to help reduce BMA residues.

[0263] The mixture was stirred overnight at 90° C. The next day, 256.90 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0264] Synthesis of Example 3

[0265] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.17 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.27 g t-butyl peroxy-2-ethylhexanoate and 2.45 g NB3043 was added over a period of 240 minutes.

[0266] 240 minutes after the start of the reaction, an additional 87.50 grams of NB3043 were added over a period of 120 minutes. At the same time, a mixture of 0.35 grams of t-butyl peroxy-2-ethylhexanoate and 3.15 grams of NB3043 were added over a period of 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 grams of LMA and 2.60 grams of SMA were added to the tail to help reduce BMA residues.

[0267] The mixture was stirred overnight at 90° C. The next day, 256.90 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0268] Synthesis of Example 4

[0269] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.15 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.28 g t-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over a period of 240 minutes.

[0270] 240 minutes after the start of the reaction, an additional 88.40 grams of NB3043 were added over a period of 120 minutes. At the same time, a mixture of 0.35 grams of t-butyl peroxy-2-ethylhexanoate and 3.15 grams of NB3043 were added over a period of 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 grams of LMA and 2.60 grams of SMA were added to the tail to help reduce BMA residues.

[0271] The mixture was stirred overnight at 90° C. The next day, 259.50 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0272] Synthesis of Example 5

[0273] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.16 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.27 g t-butyl peroxy-2-ethylhexanoate and 2.45 g NB3043 was added over a period of 240 minutes.

[0274] 240 minutes after the start of the reaction, an additional 87.50 grams of NB3043 were added over a period of 120 minutes. At the same time, a mixture of 0.35 grams of t-butyl peroxy-2-ethylhexanoate and 3.15 grams of NB3043 were added over a period of 180 minutes. 60 minutes after the start of the second feed, a mixture of 1.10 grams of LMA and 2.60 grams of SMA were added to the tail to help reduce BMA residues.

[0275] The mixture was stirred overnight at 90° C. The next day, 256.90 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0276] Synthesis of Example 6 (Comparison)

[0277] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.16 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.27 g t-butyl peroxy-2-ethylhexanoate and 2.46 g NB3043 was added over a period of 240 minutes.

[0278] 240 minutes after the start of the reaction, another 87.5 g of NB3043 was added over a period of 120 minutes. At the same time, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over a period of 180 minutes.

[0279] The mixture was stirred overnight at 90° C. The next day, 256.90 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0280] Synthesis of Example 7 (Comparison)

[0281] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.16 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.27 g t-butyl peroxy-2-ethylhexanoate and 2.46 g NB3043 was added over a period of 240 minutes.

[0282] 240 minutes after the start of the reaction, another 87.50 g of NB3043 was added over a period of 120 minutes. At the same time, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over a period of 180 minutes.

[0283] The mixture was stirred overnight at 90° C. The next day, 256.90 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0284] Synthesis of Example 8 (Comparison)

[0285] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.16 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.27 g t-butyl peroxy-2-ethylhexanoate and 2.46 g NB3043 was added over a period of 240 minutes.

[0286] 240 minutes after the start of the reaction, another 87.50 g of NB3043 was added over a period of 120 minutes. At the same time, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over a period of 180 minutes.

[0287] The mixture was stirred overnight at 90° C. The next day, 256.90 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0288] Synthesis of Example 9 (Comparative)

[0289] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.20 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.26 g t-butyl peroxy-2-ethylhexanoate and 2.35 g NB3043 was added over a period of 240 minutes.

[0290] 240 minutes after the start of the reaction, another 87.50 g of NB3043 was added over a period of 120 minutes. At the same time, a mixture of 0.35 g of tert-butyl peroxy-2-ethylhexanoate and 3.15 g of NB3043 was added over a period of 180 minutes.

[0291] The mixture was stirred overnight at 90° C. The next day, 257.00 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0292] Synthesis of Example 10

[0293] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.95 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting of 0.10 g MM (70% in NB 3020), 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 t-butyl peroxy-2-ethylhexanoate in 1.40 g NB3043, 56.90 g NB3043 and 20.80 g Group II / III oil was added over a period of 180 minutes.

[0294] 240 minutes after the start of the reaction, an additional 87.50 grams of NB3043 and 0.35 grams of t-butyl peroxy-2-ethylhexanoate in 3.15 grams of NB3043 were added over a period of 180 minutes. 120 minutes after the addition, 0.35 grams of t-butyl peroxy-2-ethylhexanoate was added.

[0295] The mixture was stirred overnight at 90° C. The next day, 256.20 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0296] Synthesis of Example 11

[0297] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.87 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting of 0.10 g MM (70% in NB 3020), 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 t-butyl peroxy-2-ethylhexanoate in 1.47 g NB3043, 59.70 g NB3043 and 21.80 g Group II / III oil was added over a period of 180 minutes.

[0298] 240 minutes after the start of the reaction, an additional 87.50 grams of NB3043 and 0.35 grams of t-butyl peroxy-2-ethylhexanoate in 3.15 grams of NB3043 were added over a period of 180 minutes. 120 minutes after the addition, 0.35 grams of t-butyl peroxy-2-ethylhexanoate was added.

[0299] The mixture was stirred overnight at 90° C. The next day, 256.20 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0300] Synthesis of Example 12

[0301] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.87 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting of 0.10 g MM (70% in NB 3020), 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 t-butyl peroxy-2-ethylhexanoate in 1.47 g NB3043, 59.70 g NB3043 and 21.80 g Group II / III oil was added over a period of 180 minutes.

[0302] 240 minutes after the start of the reaction, an additional 87.50 grams of NB3043 and 0.35 grams of t-butyl peroxy-2-ethylhexanoate in 3.15 grams of NB3043 were added over a period of 180 minutes. 120 minutes after the addition, 0.35 grams of t-butyl peroxy-2-ethylhexanoate was added.

[0303] The mixture was stirred overnight at 90° C. The next day, 256.20 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0304] Synthesis of Example 13

[0305] 61.39 g NB3043, 25.46 g Group II / III oil, 22.41 g MM (70% in Nexbase 3020), 0.17 g LMA, 17.32 g SMA, 7.33 g IDMA, 0.12 g styrene, 53.03 g BMA and 0.15 g MMA were placed in a 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.00 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.28 g t-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over a period of 240 minutes.

[0306] 240 minutes after the start of the reaction, another 86.83 g of NB3043 and 0.35 g of t-butyl peroxy-2-ethylhexanoate were added over a period of 90 minutes.

[0307] The mixture was stirred overnight at 90° C. The next day, 260.49 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0308] Synthesis of Example 14

[0309] 61.39 g NB3043, 25.46 g Group II / III oil, 22.42 g MM (70% in Nexbase 3020), 0.17 g LMA, 17.32 g SMA, 10.99 g IDMA, 0.12 g styrene, 48.64 g BMA and 0.15 g MMA were placed in a 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.00 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.28 g t-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over a period of 240 minutes.

[0310] 240 minutes after the start of the reaction, another 86.85 g of NB3043 and 0.35 g of t-butyl peroxy-2-ethylhexanoate were added over a period of 90 minutes.

[0311] The mixture was stirred overnight at 90° C. The next day, 259.95 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0312] Synthesis of Example 15

[0313] 61.39 g NB3043, 25.46 g Group II / III oil, 22.41 g MM (70% in Nexbase 3020), 5.25 g LMA, 12.25 g SMA, 7.33 g IDMA, 0.12 g styrene, 53.03 g BMA and 0.15 g MMA were placed in a 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.00 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.28 g t-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over a period of 240 minutes.

[0314] 240 minutes after the start of the reaction, another 86.83 g of NB3043 and 0.35 g of t-butyl peroxy-2-ethylhexanoate were added over a period of 90 minutes.

[0315] The mixture was stirred overnight at 90° C. The next day, 260.49 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0316] Synthesis of Example 16

[0317] 61.39 g NB3043, 25.46 g Group II / III oil, 22.42 g MM (70% in Nexbase 3020), 5.25 g LMA, 12.25 g SMA, 10.99 g IDMA, 0.12 g styrene, 48.64 g BMA and 0.15 g MMA were placed in a 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.00 g of a 10% solution of t-butyl peroxy-2-ethylhexanoate in NB3043 was added to start the reaction, and a mixture consisting 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 was added over a period of 180 minutes. Simultaneously, a second mixture of 0.28 g t-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over a period of 240 minutes.

[0318] 240 minutes after the start of the reaction, another 86.65 g of NB3043 and 0.35 g of t-butyl peroxy-2-ethylhexanoate were added over a period of 90 minutes.

[0319] The mixture was stirred overnight at 90° C. The next day, 259.95 grams of NB3043 were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0320] Synthesis of Example 17

[0321] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.00 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in 100N oil was added to start the reaction, and a mixture consisting of 0.09 g MM (70% in NB 3020), 0.18 g LMA, 17.32 g SMA, 1.66 g IDMA, 0.23 g styrene, 60.12 g BMA, 0.19 g MMA, 77.25 g 100N oil was added over a period of 180 minutes. At the same time, a second mixture of 0.28 g tert-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over a period of 240 minutes.

[0322] 240 minutes after the start of the reaction, an additional 87.20 grams of 100N oil and 0.35 grams of t-butyl peroxy-2-ethylhexanoate were added over a period of 90 minutes.

[0323] The mixture was stirred overnight at 90° C. The next day, 261.59 grams 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.

[0324] Synthesis of Example 18

[0325] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.00 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in 100N oil was added to start the reaction, and a mixture consisting of 5.26 g MM (70% in NB 3020), 0.18 g LMA, 17.10 g SMA, 1.64 g IDMA, 0.22 g styrene, 56.76 g BMA, 0.19 g MMA, 77.20 g 100N oil was added over a period of 180 minutes. At the same time, a second mixture of 0.28 g tert-butyl peroxy-2-ethylhexanoate and 2.56 g NB3043 was added over a period of 240 minutes.

[0326] 240 minutes after the start of the reaction, an additional 87.78 grams of 100N oil and 0.35 grams of t-butyl peroxy-2-ethylhexanoate were added over a period of 90 minutes.

[0327] The mixture was stirred overnight at 90° C. The next day, 263.34 grams of 100N oil were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0328] Synthesis of Example 19

[0329] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.00 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in 100N oil was added to start the reaction, and a mixture consisting of 0.09 g MM (70% in NB 3020), 0.18 g LMA, 17.52 g SMA, 1.68 g IDMA, 0.20 g styrene, 59.92 g BMA, 0.20 g MMA, 77.25 g 100N oil was added over a period of 180 minutes. At the same time, a second mixture of 0.28 g tert-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over a period of 240 minutes.

[0330] 240 minutes after the start of the reaction, an additional 87.36 grams of 100N oil and 0.35 grams of t-butyl peroxy-2-ethylhexanoate were added over a period of 90 minutes.

[0331] The mixture was stirred overnight at 90° C. The next day, 262.09 grams of 100N oil were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0332] Synthesis of Example 20

[0333] 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 4-necked glass flask equipped with a stirrer, a temperature sensor and a nitrogen tube and a reflux condenser. The flask was purged with nitrogen and heated to 90°C. Thereafter, 1.00 g of a 10% solution of tert-butyl peroxy-2-ethylhexanoate in 100N oil was added to start the reaction, and a mixture consisting of 0.09 g MM (70% in NB 3020), 0.18 g LMA, 17.72 g SMA, 1.70 g IDMA, 0.22 g styrene, 59.69 g BMA, 0.20 g MMA, 77.25 g 100N oil was added over a period of 180 minutes. At the same time, a second mixture of 0.28 g tert-butyl peroxy-2-ethylhexanoate and 2.51 g NB3043 was added over a period of 240 minutes.

[0334] 240 minutes after the start of the reaction, an additional 87.54 grams of 100N oil and 0.35 grams of t-butyl peroxy-2-ethylhexanoate were added over a period of 90 minutes.

[0335] The mixture was stirred overnight at 90° C. The next day, 262.61 grams of 100N oil were added to the flask and stirred at 90° C. for approximately 90 minutes before transferring the batch to a glass bottle.

[0336] The compositions of the resulting polyalkyl (meth)acrylate-based polymers are summarized in Table 1 below.

[0337] Table 1: Composition of poly(meth)acrylate based polymers prepared according to the present invention

[0338]

[0339] * ) Use C16 / 18 alkyl acrylate instead of octadecyl methacrylate

[0340] CE = Comparative Example

[0341] If not stated otherwise, the term "%" means wt. % (weight %).

[0342] Examples 1-5 and 10-20 are according to the invention. Examples 6-8 are comparative examples because they contain SMA contents above the claimed range. Example 9 is a comparative example because it contains C16 / 18 alkyl acrylate instead of alkyl methacrylate.

[0343] Typical properties of the obtained poly(meth)acrylate-based polymers, such as weight average molecular weight M w , number average molecular weight M n and their polydispersity index (PDI) are summarized in Table 2 below.

[0344] Table 2: Typical properties of polyalkyl (meth)acrylate based polymers of the present invention:

[0345]

[0346] CE = Comparative Example

[0347] The examples according to the present invention have weight average molecular weights ranging from 511,000 g / mol (Example 5) to 870,000 g / mol (Example 18).

[0348] Evaluation of VI improvers in formulations

[0349] In order to demonstrate the effect of the polyalkyl (meth)acrylate based polymer according to the present invention on the performance of the lubricating oil composition, different formulation examples A were prepared and the corresponding values ​​were measured. Formulations with API Group II 100N oil (e.g. aramcoPRIMA) and API Group II 220N (e.g. Chevron 220R) as base oils were prepared with fixed amounts of DI packages and viscosity improver concentrations as summarized in Table 3 below. These formulations are intended to meet the following industry standards / specifications: 5W-30 (SAE J300), 75W-80 (SAE J306), John Deere JD 20C, Caterpillar TO-4 SAE 30.

[0350] The combined formulation targets are summarized in the second column of Table 4 below.

[0351] The resulting viscosity improving additive content is typically between 8 and 12 wt%. Characteristic EO / UTTO formulation properties (KV40, KV100, HTHS150, Brookfield-40, MRV TP1-35, CCS-30 and KV100 (sheared)) were measured and summarized in Table 3.

[0352]

[0353]

[0354] Table 3b: 0W20 engine oil formulations including DI package in base oil blend

[0355]

[0356] The results given in Tables 3a and 3b clearly show that only lubricating oil compositions comprising the polymers according to the invention can meet the stringent requirements set forth in conjunction with several industrial specifications. They exhibit good wax control (pour point) and excellent low temperature properties (low Brookfield viscosity) while maintaining very good shear stability. Examples A1-A5 comprising polymer Examples 1-5 achieve pour points of at least -36°C and CCS values ​​below 6,600 mPas. The KV100 values ​​of formulations A1-A5 are well above the target 9.3 mm after 30 cycles of Bosch injector shear. 2 / s, meeting the requirements for SAE J300. They also meet KV100>7.1mm 2 / s, which is required to meet the SAE J306 requirements for 75W-80 formulations or to meet the JD 20C specification.

[0357] Despite using the same ratio of heavy base oil, Comparative Examples A6-A8 exhibit significantly worse CCS viscosities. PSSI and post-shear KV100 values ​​are significantly worse and do not meet stringent requirements.

[0358] The use of polymer Example 9, in which C16 / 18 alkyl acrylates are used instead of C16 / 18 alkyl methacrylates (see Example 5), leads to formulation A9, which meets the shear stability requirements, but fails to meet the low temperature requirements. The pour point is only -27°C and the formulation is solid at -40°C, i.e. the Brookfield viscosity at -40°C cannot be measured.

Claims

1. A polyalkyl (meth)acrylate-based polymer consisting of the following monomers: (a) 6 to 12% by weight of an ester of (meth)acrylic acid and 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 C5-11 alkyl methacrylate; (e) 0.2 to 18 wt% of C12-15 alkyl methacrylate, preferably LMA; (f) 2 to 19.8 wt% of C16-20 alkyl methacrylate, preferably SMA; and (g) 0 to 1% by weight of styrene monomer, The sum of components (e) and (f) is equal to or less than 20% by weight.

2. The polyalkyl (meth)acrylate-based polymer according to claim 1, wherein the weight average molecular weight is 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. An additive composition comprising: (A) 60% to 80% by weight of a base oil, and (B) 20 to 40 wt% of a polyalkyl (meth)acrylate-based polymer consisting of the following monomers: (a) 6 to 12% by weight of an ester of (meth)acrylic acid and 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 C5-11 alkyl methacrylate; (e) 0.2 to 18 wt% of C12-15 alkyl methacrylate, preferably LMA; (f) 2 to 19.8 wt% of C16-20 alkyl methacrylate, preferably SMA; and (g) 0 to 1% by weight of styrene monomer, The sum of components (e) and (f) is equal to or less than 20% by weight.

4. The additive composition according to claim 3, wherein the composition comprises 70 to 75 wt% of component (A) and 25 to 30 wt% of component (B).

5. A lubricating oil composition comprising: (A) 75 to 99.5 weight percent base oil; (B) 0.5 to 10% by weight of a polyalkyl (meth)acrylate-based polymer consisting of the following monomers: (a) 6 to 12% by weight of an ester of (meth)acrylic acid and 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 C5-11 alkyl methacrylate; (e) 0.2 to 18 wt% of C12-15 alkyl methacrylate, preferably LMA; (f) 2 to 19.8 wt% of C16-20 alkyl methacrylate, preferably SMA; and (g) 0 to 1% by weight of styrene monomer, wherein the sum of components (e) and (f) is equal to or less than 20% by weight, and (C) 0 to 15% by weight of one or more additional additives.

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

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