Acrylate-olefin copolymers as high viscosity base fluids

Abstract

To provide acrylate-olefin copolymers, a method for manufacturing these polymers, and a method for use of these copolymers as lubricant additives or synthetic base fluids in lubricant compositions containing these copolymers and lubricating oil compositions, preferably in gear oil compositions, transmission oil compositions, hydraulic oil compositions, engine oil compositions, marine oil compositions, industrial lubricating oil compositions or greases.SOLUTION: There is provided a copolymer, comprising: a monomer unit derived from at least one acrylate of formula (I); a monomer unit derived from at least one un-functionalized α-olefin of formula (II); and 0 to 22 mass% of a monomer unit that has a kinematic viscosity of 80 to 600 cSt at 100°C according to ASTM D 445 and is derived from a monomer having a linear alkyl group having more than 8 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to acrylate-olefin copolymers and methods for making these polymers. The invention is also directed to lubricant compositions containing these copolymers and to the use of these copolymers as lubricant additives or synthetic base fluids in lubricating oil compositions, preferably in gear oil compositions, transmission oil compositions, hydraulic oil compositions, engine oil compositions, marine oil compositions, industrial lubricating oil compositions, or in greases. [Background technology]

[0002] The present invention relates to the field of lubrication. A lubricant is a composition that reduces friction between surfaces. In addition to allowing freedom of movement between two surfaces and reducing mechanical wear of said surfaces, a lubricant may also prevent corrosion of said surfaces and / or prevent damage to said surfaces due to heat or oxidation. Examples of lubricant compositions include, but are not limited to, engine oils, transmission fluids, gear oils, industrial lubricants, greases, and metalworking oils.

[0003] Lubricants typically contain a base fluid and varying amounts of additives. Conventional base fluids are hydrocarbons, such as mineral oils. The terms base oil and base fluid are commonly used interchangeably. Here, base fluid is used as a general term.

[0004] A wide variety of additives may be combined with the base fluid depending on the intended use of the lubricant. Examples of lubricant additives include, but are not limited to, viscosity index improvers, thickeners, antioxidants, corrosion inhibitors, dispersants, extreme pressure additives, antifoam agents, and metal deactivators.

[0005] Typical non-polymer-based fluids are not very effective as lubricants due to their low viscosity and further reduced viscosity at higher operating temperatures. Therefore, polymer additives are used to thicken the base oil and reduce the change in viscosity with temperature. The term viscosity index (VI) is used to describe this change in viscosity with temperature. The lower the VI, the greater the change in viscosity with temperature, and vice versa. Therefore, a high VI is desirable for lubricant formulations. To improve the VI, polymer additives or viscosity index improvers (VII) may be added to the lubricant formulation.

[0006] It is well known in the art that alkyl acrylates are not recommended for use as VI improvers, and commercially available VI improvers are based on methacrylates.Although there are literature (Rashad et al. J. of Petr. Sci. and Engineering 2012, 173-177; Evin et al. J. of Sol. Chem 1994, 325-338) and patents (International Publication No. 96 / 17517 (WO 96 / 17517)), it is generally known that the performance of polyacrylates as VI improvers is inferior to that of polymethacrylates.In particular, International Publication No. 96 / 17517 (WO 96 / 17517) describes that it has been unexpectedly discovered that poly(alkyl acrylate) esters typically cannot sufficiently reduce the effect of temperature on viscosity when used in hydraulic fluids.

[0007] A drawback of adding polymer additives to lubricant formulations is that they are subject to shear stress and mechanical degradation over time. Higher molecular weight polymers are better thickeners, but are more susceptible to shear stress, which leads to polymer degradation. To reduce the amount of polymer degradation, the molecular weight of the polymer can be reduced, thereby resulting in a more shear-stable polymer. These shear-stable, low-molecular-weight polymers are no longer very effective thickeners and must be used at greater concentrations in the lubricant to achieve the desired viscosity. These low-molecular-weight polymers typically have a molecular weight of less than 20,000 g / mol and are also called synthetic high-viscosity base fluids. High-viscosity base fluids are used to increase the VI and thicken lubricant formulations with stringent shear stability requirements. A typical application is gear oils, which have very stringent requirements due to high mechanical stress and a wide temperature range during operation.

[0008] Typical products in this market are high-viscosity polyalphaolefins (PAOs) and metallocene polyalphaolefins (mPAOs), typically sold in the viscosity range of 40 to 300 cSt at 100°C (Choudary et al. Lubr. Sci. 2012, 23-44). Their key feature is good handling characteristics relative to viscosity, since these base fluids are actually polymers and have improved viscosity indexes. However, their weakness is low polarity. Due to the non-polar nature of PAO base oils, DI packaged and aged products are less soluble in the oils, which can cause various problems.

[0009] It has already been described that higher polarity is provided by copolymers of α-olefins and maleates (DE 3223694), copolymers of α-olefins and acrylates (DE 2243064), copolymers of α-olefins and methacrylates (EP 0471266) or terpolymers based on the above-mentioned monomers (WO 2020 / 078770). Alternatively, oil-compatible polyesters (WO 01 / 46350), polyalkyl(meth)acrylates (DE 102010028195), or polyvinyl ethers (US 20130165360) can be applied. A major advantage when polar, high-viscosity base fluids are used is that polar, low-viscosity fluids, such as esters, do not need to be used as compatibilizers for the polar lubricant additives. Polar, low-viscosity fluids are known to cause problems with coatings and seals, which is less of an issue with high-viscosity fluids.

[0010] Existing products, such as polyalphaolefins (PAOs), do not have the performance levels required for some applications. There is also a need to provide alternative solutions in the area of ​​industrial lubricants as well as industrial gear oils. In particular, it would be desirable to replace existing high viscosity polyalphaolefins, as these products are expensive and do not provide sufficient solubility for key formulation ingredients. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] International Publication No. 96 / 17517 [Patent Document 2] West German Patent Application Publication No. 3223694 [Patent Document 3] West German Patent Application Publication No. 2243064 [Patent Document 4] European Patent Application Publication No. 0471266 [Patent Document 5] International Publication No. 2020 / 078770 [Patent Document 6] WO 01 / 46350 [Patent Document 7] German Patent Application Publication No. 102010028195 [Patent Document 8] US Patent Application Publication No. 2013 / 0165360 [Non-patent literature]

[0012] [Non-Patent Document 1] Rashad et al. J. of Petr. Sci. and Engineering 2012, 173-177 [Non-patent document 2] Evin et al. J. of Sol. Chem 1994, 325-338 [Non-patent document 3] Choudary et al. Lubr. Sci. 2012, 23-44 [Non-patent document 4] Ullmann's Encyclopedia of Industrial Chemistry, 6th edition Summary of the Invention [Problem to be solved by the invention]

[0013] Therefore, an object of the present invention was to provide a high shear stable synthetic base fluid or lubricating oil additive that has a beneficial effect on oil solubility and component solubility, as well as low temperature performance in lubricating oil compositions. Furthermore, these novel polymers should be capable of thickening oils to the desired viscosity. These high shear stable polymers should also have a high viscosity index, a high flash point, and good thermal oxidative stability. [Means for solving the problem]

[0014] The inventors of the present invention have surprisingly found that the acrylate-olefin copolymers defined in claim 1 are useful as high shear stable lubricating oil additives or synthetic base fluids, depending on their treat rate in the lubricating composition. The acrylate-olefin copolymers according to the present invention have unexpectedly higher viscosity indexes than their methacrylate counterparts, as illustrated in the experimental section of the present invention. The inventors of the present invention have found that the side chains of the resulting polymer, which are derived not only from the acrylate monomer but also from the α-olefin, are crucial for achieving a combination of high VI and good low-temperature properties.

[0015] A first aspect of the present invention is an acrylate-olefin copolymer as defined in claim 1.

[0016] A second aspect of the invention is a method for producing these copolymers, as defined in claim 13.

[0017] A third aspect of the present invention is a lubricant composition comprising at least one base oil and at least one copolymer according to the invention, as defined in claim 14.

[0018] A fourth aspect of the present invention is the use of these copolymers as lubricant additives or synthetic base fluids in lubricating oil compositions, preferably in gear oil compositions, transmission oil compositions, hydraulic oil compositions, engine oil compositions, marine oil compositions, industrial lubricating oil compositions or in greases.

[0019] Detailed Description of the Invention Copolymers according to the invention The present invention relates to a copolymer comprising: a) Formula (I) [ka] [wherein R1 represents a linear or branched alkyl group having 6 to 12 carbon atoms], 65 to 90 mass % based on the total mass of the copolymer, b) Formula (II) [ka] wherein R2 represents a linear alkyl group having 6 to 16 carbon atoms, in an amount of 10 to 35% by weight, based on the total weight of the copolymer; c) 0 to 10% by weight of monomer units derived from at least one monomer selected from the list consisting of methacrylamides, fumarates, maleates, or mixtures thereof, based on the total weight of the copolymer. and the copolymer has a kinematic viscosity at 100°C according to ASTM D 445 of 80 to 600 cSt; and The copolymer comprises 0 to 22% by weight, based on the total weight of the copolymer, of monomer units derived from a monomer having a linear alkyl group with more than 8 carbon atoms.

[0020] According to one aspect of the present invention, the copolymer preferably contains 0 to 20% by mass, more preferably 0 to 18% by mass, of monomer units derived from a monomer having a linear alkyl group with more than 8 carbon atoms, based on the total mass of the copolymer.

[0021] According to another aspect of the present invention, it is preferred that the copolymer has a kinematic viscosity at 100°C according to ASTM D 445 of from 100 to 500 cSt, more preferably from 150 to 400 cSt according to ASTM D 445, more preferably from 150 to 350 cSt according to ASTM D 445.

[0022] According to another preferred embodiment of the present invention, the total content of monomer units derived from monomers a) and b) in the inventive copolymer amounts to a total of 90% by weight, more preferably a total of 95% by weight, even more preferably a total of 98% by weight, and most preferably a total of 100% by weight, based on the total weight of the copolymer.

[0023] According to another preferred embodiment of the present invention, the total content of monomer units derived from monomers a), b) and c) in the inventive copolymer amounts to a total of 90% by weight, more preferably a total of 95% by weight, even more preferably a total of 98% by weight and most preferably a total of 100% by weight, based on the total weight of the copolymer.

[0024] The acrylate a) of formula (I) above refers to an ester of acrylic acid with a linear or branched alcohol having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 8 to 10 carbon atoms. The term encompasses individual acrylate esters with alcohols of a particular length, as well as mixtures of acrylate esters with alcohols of different lengths.

[0025] According to one aspect of the present invention, R1 in the acrylate monomer of formula (I) is preferably a linear or branched alkyl group having 6 to 10 carbon atoms, more preferably a linear or branched alkyl group having 8 to 10 carbon atoms. Particularly preferred acrylates a) of formula (I) are 2-ethylhexyl acrylate, 2-propylheptyl acrylate, n-octyl acrylate, or mixtures thereof.

[0026] According to the present invention, the copolymer of the present invention preferably comprises 70 to 90% by mass, more preferably 75 to 90% by mass, of monomer units derived from the acrylate monomer a) of formula (I) above, based on the total mass of the copolymer.

[0027] According to the invention, it is preferred that the inventive copolymer comprises from 10 to 30% by weight, more preferably from 10 to 25% by weight, of monomer units derived from unfunctionalized α-olefins b) of formula (II), based on the total weight of the copolymer. Particularly preferred unfunctionalized α-olefins b) of formula (II) are selected from the group consisting of decene, dodecene, tetradecene, hexadecene or mixtures thereof.

[0028] According to a preferred embodiment of the invention, the copolymer has a weight average molecular weight according to DIN 55672-1 of 5000 to 30000 g / mol, preferably 7000 to 25000 g / mol, even more preferably 8000 to 20000 g / mol.

[0029] In the present invention, the mass average molecular weight (Mw) or number average molecular weight (M n ) was determined by gel permeation chromatography (GPC) using PMMA calibration standards according to DIN 55672-1 using the following measurement conditions: Eluent: tetrahydrofuran (THF) Operating temperature: 35℃ Columns: A column set consisting of four columns: two SDV 106 Å columns, one SDV 104 Å column, and one SDV 103 Å column (PSS Standards Service GmbH, Mainz, Germany), all with dimensions of 300 × 8 mm and an average particle size of 10 μm. Flow rate: 1mL / min Injection volume: 100 μL Equipment: Agilent 1100 series consisting of autosampler, pump and column oven Detector: Refractive index detector from the Agilent 1100 series.

[0030] Preferably, the copolymers of the present invention have a very low degree of crosslinking and a narrow molecular weight distribution, which further contributes to their shear resistance. The low degree of crosslinking and the narrow molecular weight are reflected in the polydispersity index of the copolymer. Preferably, the polydispersity index (PDI) of the copolymers of the present invention is in the range of 1.0 to 4.0, more preferably 1.5 to 3.5. A polydispersity index in the range of 1.0 to 3.5 is considered optimal for most industrial applications in terms of the shear resistance of the copolymer. The polydispersity index is defined as the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn).

[0031] According to a preferred embodiment of the present invention, the copolymers of the present invention have a COC flash point above 250° C. according to ASTM D92.

[0032] The copolymers of the present invention optionally comprise monomer units derived from monomer c) selected from the list consisting of methacrylamides, fumarates, maleates, or mixtures thereof. Preferably, the amount of monomer units derived from monomer c) in the resulting copolymers of the present invention is 0 to 10% by weight, preferably 0 to 7% by weight, more preferably 0 to 5% by weight, and even more preferably 0 to 3% by weight, based on the total weight of the copolymer. Particularly preferred monomers c) are di-2-ethylhexyl maleate, N-3-dimethylaminopropyl methacrylamide, di-2-ethylhexyl fumarate, or mixtures thereof.

[0033] It has surprisingly been observed that the incorporation of monomer unit c) in the copolymer allows for complete conversion of the non-functionalized α-olefin b), and therefore no final distillation step is required at the end of the copolymerization.

[0034] According to a preferred embodiment of the present invention, in addition to the monomer units derived from monomers a), b) and optionally c), the acrylate-olefin copolymer of the present invention further comprises from 0 to 10% by weight, more preferably from 0 to 6% by weight, based on the total weight of the copolymer, of monomer units derived from at least one monomer d) selected from alkyl (meth)acrylates, vinyl esters or mixtures thereof. Particularly preferred monomers d) are lauryl methacrylate (LMA), stearyl methacrylate (SMA) or vinyl laurate (VLA).

[0035] According to another preferred embodiment of the present invention, the total content of monomer units of monomers a), b), c) and d) adds up to 95% by weight, more preferably 98% by weight, even more preferably 100% by weight.

[0036] According to another preferred embodiment of the present invention, when the copolymer consists of monomer units derived from monomers a), b), optionally c) and optionally d), the copolymer comprises from 0 to 22% by weight, more preferably from 0 to 20% by weight, even more preferably from 0 to 18% by weight, of monomer units derived from monomers a), b), c) and d) having a linear alkyl group with more than 8 carbon atoms, based on the total weight of the copolymer.

[0037] According to the invention, the copolymer is a statistical copolymer having a sequence distribution of monomer units derived from monomers a) and b) and optionally monomers c) and d).

[0038] Preferred copolymers of the present invention According to a preferred embodiment of the present invention, the copolymer comprises a) Formula (I) [ka] [wherein R1 represents a linear or branched alkyl group having 8 to 10 carbon atoms], 65 to 90 mass%, more preferably 70 to 90 mass%, and even more preferably 75 to 90 mass%, based on the total mass of the copolymer, of monomer units derived from at least one acrylate of the formula b) Formula (II) [ka] wherein R2 represents a linear alkyl group having 8 to 12 carbon atoms, in an amount of 10 to 35% by weight, more preferably 10 to 30% by weight, and even more preferably 10 to 25% by weight, based on the total weight of the copolymer; c) monomer units derived from at least one monomer selected from the list consisting of methacrylamides, fumarates, maleates or mixtures thereof, in an amount of 0 to 10% by weight, more preferably 0 to 5% by weight, and even more preferably 0 to 3% by weight, based on the total weight of the copolymer; and the copolymer has a kinematic viscosity at 100°C according to ASTM D 445 of 80 to 600 cSt; and The copolymer contains 0 to 22% by mass, preferably 0 to 18% by mass, of monomer units derived from a monomer having a linear alkyl group with more than 8 carbon atoms, based on the total mass of the copolymer.

[0039] According to a preferred embodiment, the total content of monomer units of monomers a), b) and c) amounts to 95% by weight, more preferably 98% by weight, even more preferably 100% by weight, based on the total weight of the copolymer.

[0040] According to a preferred embodiment, the copolymer further comprises from 0 to 10% by weight, more preferably from 0 to 6% by weight, of monomer units derived from at least one monomer d) selected from alkyl (meth)acrylates, vinyl esters or mixtures thereof, based on the total weight of the copolymer. Particularly preferred monomers d) are lauryl methacrylate (LMA), stearyl methacrylate (SMA) or vinyl laurate (VLA).

[0041] According to a preferred embodiment, the total content of monomer units of monomers a), b), c) and d) adds up to 95% by weight, more preferably 98% by weight, even more preferably 100% by weight.

[0042] Method for producing copolymers according to the present invention According to the present invention, the above polymer can be prepared by the following steps: i) providing a monomer composition as described above; and ii) initiating radical polymerization in the monomer composition The compound is produced according to a method comprising:

[0043] 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.

[0044] The polymerization can be carried out under normal, reduced or elevated pressure.

[0045] For the radical copolymerization of olefins and acrylates, the polymerization temperature is not critical. Generally, the copolymerization temperature is in the range of 140 to 180°C, preferably 150 to 170°C.

[0046] The polymerization step ii) may be carried out with or without dilution in oil. Preferably, the polymerization step (ii) is carried out without diluent oil or any solvent.

[0047] Preferably, step (ii) includes the addition of a radical initiator. Preferably, the radical initiator is selected from di-tert-butyl peroxide or dicumyl peroxide. Preferably, the total amount of radical initiator relative to the total mass of the monomer mixture is 0.01 to 5% by mass, more preferably 0.1 to 1% by mass. Preferably, the total amount of radical initiator is added continuously throughout the course of the copolymerization reaction (ii).

[0048] Preferably, the copolymerization step (ii) is carried out by feeding the acrylate monomer a), and optionally the monomer c) or any other comonomers, together with the initiator, to the unfunctionalized α-olefin monomer b). Preferably, the total reaction time of the radical polymerization is between 2 and 5 hours, more preferably 3 hours.

[0049] In another preferred embodiment of the present invention, a third step iii) is optionally carried out, corresponding to a distillation step, to remove the unreacted α-olefin monomer b). Preferably, the remaining unreacted α-olefin monomer b) is removed by distillation using a rotary evaporator at 150°C and a pressure as low as 5 mbar. Advantageously, distillation step iii) is not required when the copolymer of the present invention comprises monomer units derived from monomer c). It has surprisingly been observed that a small amount of monomer c) (less than 10% by weight, more preferably less than 5% by weight, based on the total weight of the copolymer) increases the conversion of the olefin during copolymerization (less than 1% by weight of the remaining unreacted α-olefin b).

[0050] lubricating oil composition As indicated above, the present invention also relates to a lubricating oil composition comprising at least one base oil and at least one copolymer as defined in the present invention.

[0051] The base oils correspond to lubricant base oils, mineral, synthetic or natural, animal or vegetable oils, selected depending on their adapted / intended use.

[0052] Base oils used to formulate lubricating oil compositions according to the present invention include conventional base stocks selected from API (American Petroleum Institute) base stock categories known as Group I, Group II, Group III, Group IV, and Group V. The aforementioned Group I and II base stocks are mineral oil materials (e.g., paraffinic and naphthenic oils) having a viscosity index (or VI) of less than 120. Group I is further distinguished from Group II in that the latter contains 90% or more saturates and the former contains less than 90% saturates (i.e., 10% or more unsaturates). Group III is considered the highest level mineral base oil, having a VI of 120 or more and a saturates level of 90% or more. Preferably, the base oil included in the lubricating oil composition of the present invention is selected from the group consisting of API Group II and III base oils. Most preferably, the lubricant composition comprises an API Group III base oil. Group IV base oils are polyalphaolefins (PAOs). Group V base oils are esters and all other base oils not included in Groups I-IV. These base oils can be used individually or as a mixture.

[0053] In a preferred embodiment of the present invention, the lubricating oil composition comprises 0.1 to 99.9% by mass, preferably 1 to 95% by mass, of at least one base oil and 0.1 to 99.9% by mass, preferably 5% to 99% by mass, of at least one copolymer according to the present invention, based on the total mass of the lubricating composition.

[0054] The lubricating oil composition according to the present invention may also contain any other additional additives suitable for use in the formulation, including additional viscosity index improvers, pour point depressants, dispersants, demulsifiers, antifoam agents, lubricity additives, friction modifiers, antioxidants, detergents, dyes, corrosion inhibitors and / or odorants.

[0055] Uses for the copolymers of the present invention The present invention also relates to the use of the copolymers according to the invention as lubricant additives or synthetic base fluids in lubricating oil compositions, preferably in gear oil compositions, transmission oil compositions, hydraulic oil compositions, engine oil compositions, marine oil compositions, industrial lubricating oil compositions or in greases.

[0056] Experimental section The present invention will be further described in detail below with reference to examples and comparative examples, which are not intended to limit the scope of the present invention in any way. All percentages given in the tables below with respect to monomer or base fluid are mass percentages (wt%).

[0057] Abbreviations BF-26 Brookfield viscosity measured at -26°C BF-30 Brookfield viscosity measured at -30°C BV Volume Viscosity BV40 Volume viscosity at 40°C according to ASTM D445 BV100 Volumetric viscosity at 100°C according to ASTM D445 cSt centistokes cP centipoise DBPO Di-tert-butyl peroxide DCP Dicumyl Peroxide Dec DEHF Di-2-ethylhexyl fumarate DEHM Di-2-ethylhexyl maleate DMAPMAM N-3-Dimethylaminopropyl methacrylamide DoDec Dodecen EHA 2-Ethylhexyl Acrylate EHMA 2-Ethylhexyl Methacrylate HA Hexyl Acrylate HexDec Hexadecene Hitec (登録商標) 2030 Defoamer commercially available from Afton Hitec (登録商標)307 Commercially available DI package from Afton Hitec (登録商標) 3250 Commercially available DI package from Afton IDA Isodecyl Acrylate IDMA Isodecyl Methacrylate Ini initiator ITDA isotridecyl acrylate, commercially available from Aldrich KV Kinematic viscosity measured according to ASTM D445 KV 40 Kinematic viscosity measured at 40°C according to ASTM D445 KV 100 Kinematic viscosity measured at 100°C according to ASTM D445 LA Lauryl acrylate, dodecyl acrylate LMA Lauryl methacrylate, 73% C12, 27% C14, all linear Mn number average molecular weight MO methyl oleate Mw Mass average molecular weight nm Not measured nOA n-octyl acrylate NB3080 Nexbase® 3080; a Group III base oil from Neste with a KV100 of 7.9 cSt PAO100 Polyalphaolefin base oil with a KV100 of 100 cSt from Chevron Phillips PAO4 Polyalphaolefin base oil with KV100 of 4cSt PAO6 Polyalphaolefin base oil with KV100 of 6cSt PAO8 INEOS Durasyn 168;7.8cSt KV 100 A polyalphaolefin base oil having PAO8 I INEOS Durasyn 128;7.8cSt KV 100 A polyalphaolefin base oil having PDI polydispersity index PHA 2-propylheptyl acrylate PP pour point Priolube 3970 Ester-based fluid available from Croda RC9420 Commercially available DI package from Rheinchemie ReMo Residual monomer content SMA Stearyl Methacrylate, 35% C16, 65% C18, all linear SL KRL20 Shear loss after 20 hours of KRL measurement measured at 100°C SL KRL100 Shear loss after 100 hours of KRL measurement measured at 100°C TetDec Tetradecene VI Viscosity Index VLA Vinyl Laurate VPL 1-180 Evonik VISCOPLEX (登録商標) 1-180, Pour point depressant VPL 1-300 Evonik VISCOPLEX (登録商標) 1-300, pour point depressant Yubase 4 4cSt KV 100 Group III base oils from SK Lubricants.

[0058] Test Method KV ASTM D445 VI ASTM D2270 PP ASTM D5950 Copper Corrosion ASTM D130 Steel Corrosion DIN ISO 7120 TOST ASTM D2893 RPVOT ASTM D2272 Foaming ASTM D892 KRL CEC L-45-A-99 BF ASTM D2983 COC ASTM D92.

[0059] In the present invention, the volume viscosity (BV) of a product (a product obtained from a polymerization reaction) corresponds to the kinematic viscosity (KV) of the resulting polymerization product, measured according to ASTM D 445. Therefore, the volume viscosities of the polymers, BV40 and BV100 as shown in Tables 1, 2, 3 and 4 below, were measured as kinematic viscosities at 40°C and 100°C, respectively, according to ASTM D445. [Example]

[0060] Synthesis 1 : Pure acrylate (Example 39 * ) 1.62 g of DBPO (0.6% by weight based on the amount of acrylate) dissolved in 270.0 g of EHA was slowly fed to 30.0 g of PAO8 under nitrogen for 3 hours at 160° C. After stirring for another hour, the resulting clear, colorless polymer solution was cooled and used without further purification in further experiments.

[0061] Synthesis 2 (Meth)acrylate / olefin copolymer with distillation process (Example 8) 3.6 g of DBPO (0.3% by weight based on the monomers in the feed) dissolved in 1200 g of EHA was slowly fed to 300 g of 1-decene (0.33 molar equivalents based on the (meth)acrylate) under nitrogen at 160° C. for 3 hours. After stirring for another hour, the resulting clear, colorless polymer was cooled. Subsequently, residual decene was removed by distillation using a rotary evaporator at 150° C. and a low pressure of 5 mbar.

[0062] Synthesis 3 : Acrylate / olefin copolymer without distillation step (Example 54) 0.77 g of DBPO (0.3 wt. % relative to the monomers in the feed) dissolved in 249.3 g of EHA and 5.7 g of DEHF were slowly fed to 45.0 g of 1-tetradecene under nitrogen for 3 hours at 160° C. After stirring for another hour, the resulting clear, colorless polymer was cooled and used without further purification.

[0063] Examples 1-28 were prepared in the same manner as Synthesis 2, except that the amounts of reactants or other reaction conditions were changed as listed in Table 1. The α-olefin monomer was always charged to the reactor first, and the (meth)acrylate monomer and the initiator were fed over a set period of time.

[0064] Examples 38-43 were prepared in the same manner as Synthesis 1, except that the amounts of reactants or other reaction conditions were changed as listed in Table 3.

[0065] Examples 44-61 were prepared in the same manner as Synthesis 3, except that the amounts of reactants or other reaction conditions were changed as listed in Table 4.

[0066] Because the molar ratio in the reaction is not representative of the final composition, the final ratio of olefins in the polymer after distillation is given in mass% (olefins inc.). This ratio was determined gravimetrically, assuming that the (meth)acrylate conversion was complete or its boiling point was too high to be removed by distillation. For example, Example 8 has a residual EHA content of less than 0.01 mass% before the distillation step.

[0067] For some examples, up to three polymers with similar viscosities were blended. For the blending process, the products were stirred together at 80°C for 1 hour. The blends are listed in Table 2 (see Examples 29-37). The amount of incorporated olefin was calculated from the values ​​determined for the individual components. Other values, such as molecular weight or viscosity, were measured for the blends.

[0068] A good high viscosity base fluid must combine several properties. An important criterion for a high performance gear oil is its low temperature performance. In addition to a low dependence of the viscosity on temperature, which is also reflected in its VI, it is important that the polymer does not exhibit strong intermolecular interactions that would lead to poor low temperature performance.

[0069] The polymers according to the invention have a favorable combination of viscosity, viscosity index and shear stability as exemplified in Examples 5, 6 and 8. In contrast, Comparative Example 7, an acrylate-olefin copolymer containing 22.6 wt. % linear side chains with more than 8 carbon atoms, exhibits a viscosity index of 1.25. * has a good VI (236), but its lubricant formulation (Example F-21 * It can be observed that the acrylate-olefin copolymer of Example 50, which has only 15% by weight of linear side chains with more than 8 carbon atoms, does not perform well at low temperatures (BF-26 = 192,000 cP), as shown in Example F-28. In contrast, the acrylate-olefin copolymer of Example F-26, which has only 15% by weight of linear side chains with more than 8 carbon atoms, combines a high VI (220) and performs extremely well under even more severe low temperature conditions (BF-30 = 102,000 cP) as shown in Example F-28 (Comparative Example F-21). * (For BF-26 instead of BF-30).

[0070] Surprisingly, the longer side chains, for example in inventive examples 48 (C12 side chains) or 51 (C14 side chains), perform at the same level as example 50 (C10 side chains), because the total amount of monomer units in the copolymer derived from monomers with linear alkyl groups having more than 8 carbon atoms in total is less than 22 wt. % based on the total weight of the copolymer. The long linear side chains (more than 8 carbon atoms) are comparable to those in comparative example 13, which has 81 wt. % linear side chains of more than 8 carbon atoms due to a high content of lauryl acrylate. * It can be any monomer unit of the copolymer (any monomer a), b), c), d) or other comonomer) as shown in Figure 1. Comparative Formulation F-38 * As shown in Table 1, a high content of long linear side chains with more than 8 carbon atoms in the acrylate monomer units results in extremely poor low temperature performance (PP at -18°C) despite a high VI (195), and therefore a good combination of high VI and good low temperature performance is not achieved. The amount of these side chains is provided as ">C8 SC" in Tables 1-4.

[0071] While polymethacrylates are known to be excellent VI improvers, surprisingly, their acrylate counterparts are superior in the lower molecular weight range. This is illustrated in Table 5, where F-2 and F-3 * but based on very similar polymers (EHA for Example 29 according to the invention and Comparative Example 20 * (based on EHMA for example), but the much higher VI of the EHA-based polymer (Inventive Example 29) results in a higher VI and better low temperature viscosity of the final formulation.

[0072] F-2 is a PAO100-based compound F-1 * Compared to pure polyolefins, the polar ester functionality in the acrylate-olefin copolymers of the present invention is beneficial to the overall compatibility of the different formulation components (to allow direct comparison with PAO100, the formulations in Table 4 were prepared without additional additives). Unlike PAOs, which must be prepared by cationic or coordination polymerization methods, the radical polymerization method used to prepare the acrylate-olefin copolymers of the present invention provides easy access to more viscous products with good shear stability levels in a commercially attractive manner.

[0073] [Table 1]

[0074] [Table 2]

[0075] [Table 3]

[0076] [Table 4]

[0077] [Table 5]

[0078] Examples of formulations with EHA homopolymers can be found in Tables 6 and 7. For process reasons, the pure acrylates shown in Table 3 were prepared as solutions in oil, so bulk properties are not available for these polymers. The oil used in the polymerization was the same as that used later in the formulation, so as not to affect the comparison of the copolymers. As can be seen, the listed EHA homopolymers (Comparative Example 38) * and 39 * ) have a lower VI in the formulation and show poorer low temperature performance. As shown in Table 8, comparative polyacrylate examples with longer side chains as the EHA homopolymer also do not perform as well as the inventive acrylate-olefin copolymers of the present invention.

[0079] [Table 6]

[0080] [Table 7]

[0081] [Table 8]

[0082] [Table 9]

[0083] High performance lubricants also need to meet many requirements, especially good low temperature properties, high flash point and good aging behavior, which are directly influenced by the choice of high viscosity base fluid.

[0084] Table 10 below shows that the inventive acrylate-olefin copolymers of this invention have high flash points and meet the requirements for gear oil applications.

[0085] The effect of different PAO viscosity grades is shown in Table 11 below (PAO4, PAO6, PAO8). Lower grades, such as PAO4, allow for the use of higher amounts of the acrylate-olefin copolymer of the present invention, which further improves the VI and low-temperature performance of the resulting formulation. Inventive formulation F-23 provides additional performance parameters important for industrial gear oil formulations. Its strong performance in the TOST and RPVOT tests indicates good stability against severe thermo-oxidative stress. The formulation's low foaming tendency and low corrosivity highlight the suitability of the acrylate-olefin copolymer of the present invention in gear oil formulations.

[0086] [Table 10]

[0087] [Table 11]

[0088] The performance of the polymer without the distillation step is shown in Tables 12 and 13 below and is at a similar level to the distilled sample (Table 1). Caution must be exercised in comparing the different formulations in PAO8 because two different samples were used. "PAO8" has excellent low-temperature properties, while "PAO8 I" exhibits slightly inferior low-temperature properties with improved VI levels.

[0089] [Table 12]

[0090] [Table 13]

[0091] A preferred embodiment of the present invention is as follows: 1. A copolymer comprising: a) Formula (I) [ka] [wherein R1 represents a linear or branched alkyl group having 6 to 12 carbon atoms], 65 to 90 mass % based on the total mass of the copolymer, b) Formula (II) [ka] wherein R2 represents a linear alkyl group having 6 to 16 carbon atoms, in an amount of 10 to 35% by weight, based on the total weight of the copolymer; and c) 0 to 10% by weight of monomer units derived from at least one monomer selected from the list consisting of methacrylamides, fumarates, maleates or mixtures thereof, based on the total weight of the copolymer. and the copolymer has a kinematic viscosity of 80 to 600 cSt at 100°C according to ASTM D 445; and the copolymer comprises 0 to 22% by weight, based on the total weight of the copolymer, of monomer units derived from a monomer having a linear alkyl group with more than 8 carbon atoms; The copolymer.

[0092] 2. The copolymer according to 1., wherein the copolymer comprises 0 to 20% by weight, preferably 0 to 18% by weight, of monomer units derived from a monomer having a linear alkyl group with more than 8 carbon atoms, based on the total weight of the copolymer.

[0093] 3. The copolymer according to 1. or 2., wherein the copolymer has a kinematic viscosity at 100°C according to ASTM D 445 of 100 to 500 cSt, preferably 150 to 400 cSt according to ASTM D 445, and more preferably 150 to 350 cSt according to ASTM D 445.

[0094] 4. The copolymer according to any one of 1. to 3., wherein the copolymer comprises from 10 to 30% by weight, preferably from 10 to 25% by weight, of monomer units b) derived from the unfunctionalized α-olefin of formula (II) above, based on the total weight of the copolymer.

[0095] 5. The copolymer according to any one of 1. to 4., wherein the unfunctionalized α-olefin b) of formula (II) is selected from the group consisting of decene, dodecene, tetradecene, hexadecene, or a mixture thereof.

[0096] 6. The copolymer according to any one of 1. to 5., wherein R1 in the acrylate of formula (I) is a linear or branched alkyl group having 6 to 10 carbon atoms, preferably 8 to 10 carbon atoms, and even more preferably the acrylate of formula (I) is selected from 2-ethylhexyl acrylate, 2-propylheptyl acrylate, n-octyl acrylate, or a mixture thereof.

[0097] 7. The copolymer according to any one of 1. to 6., wherein the copolymer contains 0 to 7% by mass, preferably 0 to 5% by mass, and more preferably 0 to 3% by mass of monomer units derived from monomer c), based on the total mass of the copolymer.

[0098] 8. A copolymer according to any one of 1. to 7., wherein the total amount of monomer units derived from monomers a) and b) in the copolymer is 90% by mass, preferably 95% by mass, and even more preferably 98% by mass, based on the total mass of the copolymer.

[0099] 9. The copolymer according to any one of 1. to 8., wherein the total amount of monomer units derived from monomers a), b) and c) in the copolymer totals 90% by mass, preferably 95% by mass, more preferably 98% by mass, and most preferably 100% by mass, based on the total mass of the copolymer.

[0100] 10. The copolymer according to any one of 1. to 9., wherein the copolymer has a weight average molecular weight according to DIN 55672-1 of 5000 to 30000 g / mol, preferably 7000 to 25000 g / mol, and even more preferably 8000 to 20000 g / mol.

[0101] 11. The copolymer according to any one of 1. to 10., wherein the copolymer has a PDI of 1 to 4, preferably 1.5 to 3.5.

[0102] 12. The copolymer according to any one of 1. to 11., wherein the copolymer has a COC flash point greater than 250°C according to ASTM D92.

[0103] 13. A method for producing a copolymer as defined in any one of 1. to 12., said method comprising the steps of: i) providing a monomer composition; ii) initiating radical polymerization in the monomer composition to obtain the copolymer. The method comprising:

[0104] 14. A lubricant composition comprising one or more base oils and at least one copolymer according to any one of 1. to 12.

[0105] 15. Use of a copolymer as defined in any of 1. to 12. in a lubricating oil composition, preferably in a gear oil composition, transmission oil composition, hydraulic oil composition, engine oil composition, marine oil composition, industrial lubricating oil composition or in a grease, as a lubricant additive or synthetic base fluid.

Claims

1. A copolymer comprising: a) Formula (I) 【Chemical 1】 [In the formula, R １ means a linear or branched alkyl group having 6 to 12 carbon atoms], 65 to 90% by weight, based on the total weight of the copolymer; b) Formula (II) 【Chemistry 2】 [In the formula, R ２ means a linear alkyl group having 6 to 16 carbon atoms], 10 to 35% by weight, based on the total weight of the copolymer; and c) monomer units derived from at least one monomer selected from the list consisting of methacrylamides, fumarates, maleates or mixtures thereof, from 0 to 10% by weight, based on the total weight of the copolymer; and the copolymer has a kinematic viscosity of 80 to 600 cSt at 100°C according to ASTM D 445; and the copolymer comprises 0 to 22 weight percent, based on the total weight of the copolymer, of monomer units derived from monomers having a linear alkyl group with more than 8 carbon atoms; The copolymer.

2. 10. The copolymer of claim 1, wherein the copolymer comprises 0 to 20 weight percent, based on the total weight of the copolymer, of monomer units derived from monomers having a linear alkyl group with more than 8 carbon atoms.

3. 3. The copolymer of claim 1 or 2, wherein the copolymer has a kinematic viscosity according to ASTM D 445 at 100° C. of 100 to 500 cSt.

4. 4. The copolymer according to claim 1, wherein the copolymer comprises from 10 to 30% by weight of monomer units b), derived from the non-functionalized α-olefin of formula (II), based on the total weight of the copolymer.

5. 5. The copolymer of claim 1, wherein the unfunctionalized α-olefin b) of formula (II) is selected from the group consisting of decene, dodecene, tetradecene, hexadecene, or mixtures thereof.

6. R in the acrylate of formula (I) １ 6. The copolymer of claim 1, wherein is a linear or branched alkyl group having from 6 to 10 carbon atoms.

7. 7. The copolymer according to claim 1, wherein the copolymer comprises 0 to 7% by weight of monomer units derived from monomer c), based on the total weight of the copolymer.

8. 8. The copolymer according to claim 1, wherein the total amount of monomer units derived from monomers a) and b) in the copolymer totals 90% by weight, based on the total weight of the copolymer.

9. 9. The copolymer according to claim 1, wherein the total amount of monomer units derived from monomers a), b) and c) in the copolymer totals 90% by weight, based on the total weight of the copolymer.

10. 10. The copolymer according to claim 1, wherein the copolymer has a weight average molecular weight according to DIN 55672-1 of 5000 to 30000 g / mol.

11. 11. The copolymer of any one of claims 1 to 10, wherein the copolymer has a PDI of 1 to 4.

12. 12. The copolymer of claim 1, wherein the copolymer has a COC flash point according to ASTM D92 greater than 250°C.

13. 13. A method for producing a copolymer as defined in any one of claims 1 to 12, said method comprising the steps of: i) providing a monomer composition; ii) initiating radical polymerization in the monomer composition to obtain the copolymer. The method comprising:

14. 13. A lubricant composition comprising one or more base oils and at least one copolymer according to any one of claims 1 to 12.

15. 13. Use of a copolymer as defined in any one of claims 1 to 12 as a lubricant additive in a lubricating oil composition or in a grease or synthetic base fluid.

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