JP2024024934A - Copper corrosion inhibitor composition for automotive industry - Google Patents

Abstract

To provide a composition for inhibiting or reducing copper corrosion of copper-containing metal parts consisting of or containing copper, and a method for inhibiting or reducing the copper corrosion in the automotive industry, particularly in an e-mobility market.SOLUTION: The composition comprises at least one base oil and at least one nitrogen-functionalized poly-alkyl (meth)acrylate.SELECTED DRAWING: None

Description

The present invention provides at least one base oil and at least one nitrogen-functionalized polyalkyl (meth)acrylate for inhibiting or reducing copper corrosion of metal parts made of or containing copper. and a method for inhibiting or reducing copper corrosion in the automotive industry, particularly in the e-mobility market.

Polyalkyl (meth)acrylate copolymers can be used as viscosity index improvers (VII) or pour point depressants (PPD) with excellent viscosity index (VI) improving properties, shear stabilizing properties, and solubility in base oils. Widely used. Accordingly, lubricants, dielectric fluids, coolants, fuels, etc. containing polyalkyl (meth)acrylate copolymers are known to exhibit excellent viscosity index and shear stability, thus saving fuel. . They also have a long service life.

Nevertheless, there is always a strong demand for further improvements. Particularly in the growing market of electric and hybrid vehicles, additives that can not only achieve superior VI and shear resistance of fluids that can be used in mechanical and electrical equipment, but also prevent corrosion of their metal parts, are desirable.

In particular, the demand for corrosion inhibition of copper-containing metals or alloys, i.e., copper corrosion inhibition, is particularly strong in E -Increasing in the mobility field. These fluids are, for example, lubricants, dielectric fluids, coolants, fuel or gear and axle fluids, electric vehicle transmission fluids, fluids for batteries or other electrical equipment systems. Currently, temperatures in electrical equipment found in vehicles, such as batteries, electric motors, transformers, capacitors, liquid-filled transmission lines, liquid-filled power cables, computers and power electronics, may rise rapidly with use; And challenge the equipment materials. Since the above-mentioned fluids may come into contact with the yellow metal, protection of said metal at high temperatures, for example above 130° C., is required.

US Pat. No. 4,012,408 A1 discloses a lubricating oil that complies with ASTM D130 but has excellent copper corrosion inhibition as measured by a 3 hour copper plate corrosion test at a standard temperature of 120°C. According to US Pat. No. 4,012,408, dithiothiazoles are used as additives for this purpose.

In a similar manner, WO2015/171364A1 describes lubrication in gear and driveline equipment using a mixture of N-hydrocarbyl substituted amino esters and substituted thiadiazoles at 160°C for 168 h according to ASTM D130. Copper corrosion protection in agent formulations is disclosed.

US Patent Application Publication No. 2018/0201863 (US 2018/0201863) describes composite copolymers of ethylenically unsaturated mono- or dicarboxylic acids and α-olefins for corrosion protection in general. . Cu corrosion is mentioned as an example of corrosion in said specification, but US Patent Application Publication No. 2018/0201863 is tested in a test that does not involve application at temperatures higher than 130 °C. , focuses on steel corrosion. Said document does not mention, in particular, the temperature rise and the lifetime required for practical use.

In the Journal of Applied Polymer Science (B. Mueller, D. Triantafillidis, Polymeric Corrosion Inhibitors for Copper and Brass Pigments, Vol. 80, 2001, pp. 475-483), the authors Discuss. Some low molecular weight styrene-maleic acid copolymers have been described as effective corrosion inhibitors. It is stated that low acid numbers are necessary, but not sufficient for corrosion inhibition. Additionally, it has been stated that increasing copolymer loading results in increased corrosion inhibition. However, according to this article, polyacrylic acid, polyvinyl alcohol and high molecular weight styrene-maleic acid copolymers are ineffective. The most effective group of polymers tested in this study are copolymers consisting of acrylate and styrene monomer units.

US Patent No. 4012408 International Publication No. 2015/171364 US Patent Application Publication No. 2018/0201863 US Patent No. 4,316,973 Japanese Patent Application Publication No. 175096/1983 British Patent Application No. 2270317 International Publication No. 96/30421 International Publication No. 97/47661 International Publication No. 97/18247 International Publication No. 98/40415 International Publication No. 99/10387 International Publication No. 98/01478 International Publication No. 2004/083169 European Patent Application No. 0776959 European Patent Application No. 0668342 International Publication No. 97/21788 International Publication No. 00/15736 International Publication No. 00/14188 International Publication No. 00/14187 International Publication No. 00/14183 International Publication No. 00/14179 International Publication No. 00/08115 International Publication No. 99/41332 European Patent Application No. 1029029 International Publication No. 01/18156 International Publication No. 01/57166 International Publication No. 2013/189951

Journal of Applied Polymer Science (B. Mueller, D. Triantafillidis, Polymeric Corrosion Inhibitors for Copper and Brass Pigments, Vol. 80, 2001, pp. 475-483) Ullmann's Encyclopedia of Industrial Chemistry, 6th edition J.-S. Wang, et al., J. Am. Chem. Soc, vol. 117, p. 5614-5615 (1995), Matyjaszewski, Macromolecules, vol. 28, p. 7901-7910 (1995) T. Mang, W. Dresel (eds.): “Lubricants and Lubrication”, Wiley-VCH, Weinheim 2001 R. M. Mortier, S. T. Orszulik (eds.): “Chemistry and Technology of Lubricants”

Correspondingly, it is possible to suppress copper corrosion of metals at high temperatures, for example above 130 °C, while still having excellent viscosity index improvement, solubility and shear stability properties for the automotive industry, in particular for e-mobility. There continues to be a need to develop new additives for fluids on the market, such as lubricants, dielectric fluids, coolants and fuels.

Polyalkyl (meth)acrylates based on nitrogen-functionalized polyalkyl (meth)acrylate (PAMA) copolymers or polybutadiene-based macromonomers provide excellent copper corrosion control and thus are useful in mechanical or electrical devices, e.g. Electrical equipment in the automotive industry, in particular for the growing e-mobility market or in vehicles, such as batteries, electric motors, electric vehicle transmissions, transformers, capacitors, liquid-filled transmission lines, liquid-filled power cables, computers and as copper corrosion inhibitors (yellow metal passivators) in lubricants, dielectric fluids, coolants or fuels that may be used in power electronics.

More specifically, the inventors of the present invention have proposed that a composition containing at least one base oil and at least one polymer according to the invention can be used in fluids that come into direct contact with metal parts of mechanical or electrical equipment. It has been found that copper corrosion is significantly suppressed when used as

The compositions of the invention are presently present in particular in corrosion inhibition tests, such as the copper plate test according to ASTM D130 (standard test method for the corrosiveness of petroleum products to copper, which is usually carried out at 100-120°C). Exhibits excellent copper corrosion inhibition at higher temperatures than those of The compositions of the present invention exhibit a great copper corrosion protection effect at temperatures of 130-240°C, preferably 130-200°C, more preferably 150-200°C, while being compatible with various bases such as polymers known from the prior art. Maintains good solubility in oil, viscosity index improving properties, and shear stability improving properties.

Accordingly, in a first aspect, the invention relates to a composition comprising one or more base oils and one or more polyalkyl (meth)acrylates as defined in claim 1.

In a second aspect, the invention provides for copper corrosion of metal parts consisting of or containing copper within a temperature range of 130-240°C, preferably 130-200°C, more preferably 150-200°C. Related to methods for suppressing or reducing.

DETAILED DESCRIPTION OF THE INVENTION In the following, the invention will be described in detail.

In a first aspect, the invention provides a method for preventing or suppressing copper corrosion of at least one metal component, preferably consisting of or containing copper, within a temperature range of 130 to 240°C. It relates to a composition for:
Based on the total weight of monomers in the (A) one or more base oils and (B) monomer composition:
(a) 1 to 35% by weight, preferably 1.5 to 30% by weight, more preferably 2 to 30% by weight of one or more nitrogen-containing ethylenically unsaturated monomers;
(b) 40-99% by weight, preferably 45-98% by weight of one or more monomers selected from the group consisting of linear, branched and cyclic C ₁ -C ₄₀ alkyl (meth)acrylates, and ( c) 0-45% by weight, preferably 0-40% by weight of one or more polybutadiene macromonomers having a number average molecular weight measured according to DIN 55672-1 of 500-10 000 g/mol
one or more polyalkyl (meth)acrylates obtainable by radical polymerization of a monomer composition comprising:

Preferably, said nitrogen-containing ethylenically unsaturated monomer(s) (a) are:
(a1) aminoalkyl (meth)acrylate and aminoalkyl (meth)acrylamide,
(a2) nitrogen-functionalized (meth)acrylic acid derivatives having at least one cyano or nitrile group and (meth)acrylates derived from ketones,
(a3) a nitrogen-functionalized (meth)acrylate having at least one further carbonyl group;
(a4) nitrogen-functionalized cyclic (meth)acrylate,
(a5) a nitrogen-functionalized cyclic vinyl compound,
or mixtures thereof.

More preferably, said nitrogen-containing ethylenically unsaturated monomer (a) is:
(a1) N-(3-dimethylaminopropyl)methacrylamide, 3-diethylaminopentyl (meth)acrylate, 3-dimethylaminoethyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylate, 3-dibutyl-aminohexa Decyl (meth)acrylate,
(a2) N-(methacryloyloxyethyl)diisobutylketimine, N-(methacryloyloxyethyl)dihexadecylketimine, (meth)acryloylamide acetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethyl(meth)acrylate,
(a3) N-(methacryloyloxy)-formamide, N-methacryloyl-2-pyrrolidinone, N-(2-methacryloyloxyethyl)-2-pyrrolidinone, N-(3-methacryloyloxy-propyl)-2-pyrrolidinone, N -(2-methacryloyloxypentadecyl)-2-pyrrolidinone, N-(3-methacryloyloxyheptadecyl)-2-pyrrolidinone,
(a4) 2-(1-imidazolyl)ethyl (meth)acrylate, 2-(4-morpholinyl)ethyl (meth)acrylate, oxazolidinylethyl (meth)acrylate and N-methacryloylmorpholine,
(a5) 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9- Vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinyl selected from the group consisting of caprolactam, N-vinylbutyrolactam or mixtures thereof.

Even more preferably, said one or more nitrogen-containing ethylenically unsaturated monomers (a) are from the group consisting of N-3-dimethylaminopropyl methacrylamide, N-vinylpyrrolidone, dimethylaminoethyl methacrylate or mixtures thereof. selected.

In the context of the present invention, the term "one or more" means "one or a mixture thereof".

Further details of the polymers used in the composition are provided below:
Polyalkyl (meth)acrylates of the Invention The polyalkyl (meth)acrylates of the invention, based on the total weight of monomers in the monomer composition, have the following:
(a) 1 to 35% by weight, preferably 1.5 to 30% by weight, more preferably 2 to 30% by weight of one or more nitrogen-containing ethylenically unsaturated monomers;
(b) 40-99% by weight, preferably 45-98% by weight of one or more monomers selected from the group consisting of linear, branched and cyclic C ₁ -C ₄₀ alkyl (meth)acrylates, and ( c) one or more polybutadiene macromonomers 0 to 45 having a number average molecular weight measured according to DIN 55672-1 of 500 to 10 000 g/mol, preferably 1000 to 6000 g/mol, more preferably 1500 to 5500 g/mol % by weight, preferably 0-40% by weight
It can be obtained by radical polymerization of a monomer composition containing.

As used herein, the term "polybutadiene-based macromonomer(s)" refers to the reaction product of transesterification of an ester of (meth)acrylic acid with a hydroxylated hydrogenated polybutadiene; Refers to an ester of (meth)acrylic acid, which is any reaction product of the direct esterification of acrylic acid with hydroxylated hydrogenated polybutadiene. The polybutadiene macromonomer(s) of the present invention may also be referred to below as MM ( Macro Monomer).

The term "(meth)acrylate" as used herein refers to one or more esters of acrylic acid, one or more esters of methacrylic acid, or a mixture of esters of acrylic acid and methacrylic acid.

The term "(meth)acrylic acid" as used herein refers to acrylic acids, methacrylic acids, and mixtures of acrylic and methacrylic acids.

According to the invention, said polyalkyl (meth)acrylate(s) comprises a composition containing at least said monomer (a) and said monomer (b), but not said monomer (c). obtained from. This type of polyalkyl (meth)acrylate may also be referred to below as PAMA polymer or PAMA.

Alternatively, said polyalkyl (meth)acrylate(s) is obtained from a composition containing at least said monomer (a), said monomer (b) and said monomer (c). This type of polyalkyl (meth)acrylate is also referred to below as polybutadiene-containing PAMA polymer, polybutadiene-containing PAMA or polyalkyl (meth)acrylate based on polybutadiene-based macromonomers. A polybutadiene-containing PAMA polymer in the context of the present invention comprises a first polymer, also called a backbone or main chain, and a number of further polymers, called side chains, which are covalently bonded to said backbone. In this case, the skeleton of the polymer is formed by the linked unsaturated groups of the (meth)acrylic ester. The alkyl group of the (meth)acrylic ester and the hydrogenated polybutadiene chain form the side chain of the polymer. Reaction product of one ester of (meth)acrylic acid and one hydroxylated hydrogenated polybutadiene or reaction product of one (meth)acrylic acid and one hydroxylated hydrogenated polybutadiene The compound corresponds to monomer (c) and is also referred to as a macromonomer or a polybutadiene-based macromonomer in the present invention.

The polyalkyl (meth)acrylates according to the invention, whether they are PAMA polymers or polybutadiene-containing PAMA polymers, have a molecular weight of 5000 to 300 000 g/mol, preferably 8 000 to 280 000 g/mol, more preferably 10 000 to 250 000 g/mol. It has a weight average molecular weight (M _w ) of mol.

According to the invention, the weight average molecular weight (M _w ) and number average molecular weight (M _n ) of said polymers are determined by gel permeation chromatography (GPC) according to DIN 55672-1 and for PAMA polymers by poly(methyl methacrylate) ( PMMA) calibration standards and polystyrene calibration standards for polybutadiene-containing PAMA polymers and are determined using the following measurement conditions:
Eluent: Tetrahydrofuran (THF) containing 0.02M 2-diethylaminoethylamine
Operating temperature: 35℃
Columns: The column set consists of one precolumn (SDV 10μ, 8x50mm) and four columns: SDV 10 ⁶ Å, SDV 10 ⁵ Å and 2x SDV 10 ³ Å (PSS Standards Service GmbH, Mainz, Germany). ), all four columns have a size of 300 x 8 mm and an average particle size of 10 μm.
Flow rate: 1mL/min
Injection volume: 100μL
Equipment: Agilent 1100 series consisting of autosampler, pump and column oven Detection equipment: Refractive index detector from the Agilent 1260 series.

Preferably, the polydispersity index (PDI) of the polymer according to the invention is between 1.0 and 6.0, preferably between 1.2 and 4.0, more preferably between 1.5 and 3.5, even more preferably between 1 It is within the range of .5 to 3.2. The polydispersity index is defined as the ratio of weight average molecular weight to number average molecular weight (M _w /M _n ).

The polybutadiene-containing PAMA polymers according to the invention can also be characterized by their molar degree of branching ("f-branching"). The molar degree of branching refers to the percentage of the macromonomer (monomer (c)) in mol% based on the total molar amount of all the monomers in the monomer composition. The molar amount of macromonomer used is calculated based on the number average molecular weight M _n of said macromonomer. The calculation of the degree of molar branching is described in detail in WO 2007/003238 A1, which is expressly referred to herein, in particular on pages 13 and 14.

Preferably, the polybutadiene-containing PAMA polymer has a molar degree of _branching f of 0.1 to 5 mol%, more preferably 1.5 to 4 mol% and most preferably 1.5 to 2.5 mol%.

In the experimental section below, it was confirmed in the test results that the polymers of the present invention had much better ratings for the copper plate test than untreated base oils or base oils treated with state-of-the-art corrosion inhibitors. have been shown to have significant effects in inhibiting or reducing copper corrosion at high temperatures. Accordingly, the polymers of the present invention have been shown to be effective copper corrosion inhibitors for preventing, inhibiting or reducing copper corrosion in metal parts.

Advantageously, the polymers according to the invention not only efficiently suppress copper corrosion in metal parts, but also exhibit a compatible low electrical conductivity even at high concentrations, which makes them suitable for use in e-mobility applications. Makes use extremely beneficial.

Monomer (a) :
According to the invention, one or more nitrogen-containing ethylenically unsaturated monomers are present in said monomer composition as monomer (a) in an amount of 1 to 35% by weight, preferably based on the total weight of said monomer composition. It is included in an amount of 1.5 to 30% by weight, more preferably 2 to 30% by weight.

As used herein, a "nitrogen-containing ethylenically unsaturated monomer" may also be referred to herein as a "nitrogen-functionalized monomer."

Preferably, the monomer (a) according to the invention is:
(a1) aminoalkyl (meth)acrylate and aminoalkyl (meth)acrylamide,
(a2) (meth)acrylates derived from nitrogen-functionalized (meth)acrylic acid derivatives and ketones having at least one cyano group;
(a3) a nitrogen-functionalized (meth)acrylate having at least one further carbonyl group;
(a4) nitrogen-functionalized cyclic (meth)acrylate,
(a5) a nitrogen-functionalized cyclic vinyl compound,
or a mixture thereof.

More preferably, the monomer (a1) is N-(3-dimethylaminopropyl) methacrylamide (DMAPMA), 3-diethylaminopentyl (meth)acrylate, 3-dimethylaminoethyl (meth)acrylate (DMAEMA), 3- selected from the group consisting of dimethylaminopropyl (meth)acrylate, 3-dibutyl-aminohexadecyl (meth)acrylate, or mixtures thereof.

More preferably, the monomer (a2) is N-(methacryloyloxyethyl)diisobutylketimine, N-(methacryloyloxyethyl)dihexadecylketimine, (meth)acryloylamide acetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethyl( meth)acrylates, or mixtures thereof.

More preferably, the monomer (a3) is N-(methacryloyloxy)-formamide, N-methacryloyl-2-pyrrolidinone, N-(2-methacryloyloxyethyl)-2-pyrrolidinone, N-(3-methacryloyloxy- (propyl)-2-pyrrolidinone, N-(2-methacryloyloxypentadecyl)-2-pyrrolidinone, N-(3-methacryloyloxyheptadecyl)-2-pyrrolidinone, or mixtures thereof.

More preferably, the monomer (a4) is 2-(1-imidazolyl)ethyl (meth)acrylate, 2-(4-morpholinyl)ethyl (meth)acrylate, oxazolidinylethyl (meth)acrylate and N-methacryloyl selected from the group consisting of morpholine, or mixtures thereof.

Preferably, the monomer (a5) is 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinyl Pyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone (NVP), 2-vinylpyrrolidone, N-vinyl selected from the group consisting of pyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, or mixtures thereof.

More preferably, the nitrogen-containing ethylenically unsaturated monomer (a) according to the invention is selected from the group consisting of NVP, DMAEMA, DMAPMA or mixtures thereof.

Monomer (b) :
According to the invention, linear, branched and cyclic C ₁ -C ₄₀ alkyl (meth)acrylates, preferably C ₁ -C ₃₀ alkyl (meth)acrylates, more preferably C ₁ -C ₂₀ alkyl (meth)acrylates, One or more monomers selected from the group consisting of acrylates are present in the monomer composition as monomer (b) from 40 to 99% by weight, preferably from 45 to 98% by weight, based on the total weight of the monomer composition. Contained in an amount of % by weight.

The term "C ₁ -C ₄₀ alkyl (meth)acrylate" as used herein refers to an ester of (meth)acrylic acid with a linear, branched or cyclic alcohol having from 1 to 40 carbon atoms. say. The term includes individual (meth)acrylic esters with alcohols of specific lengths, as well as mixtures of (meth)acrylic esters with alcohols of different lengths.

Similarly, the term "C ₁ -C ₃₀ alkyl (meth)acrylate" as used herein refers to (meth)acrylic acid and linear, branched or cyclic alcohols having from 1 to 30 carbon atoms. and as used herein, the term "C ₁ -C ₂₀ alkyl (meth)acrylate" refers to (meth)acrylic acid and a linear, branched or cyclic ester having from 1 to 20 carbon atoms. An ester with an alcohol.

According to the invention, monomer (b) may be a single or one alkyl (meth)acrylate monomer or an alkyl selected from the above-mentioned group of monomers that may be used as said monomer (b). It may also represent a mixture of (meth)acrylate monomers.

Examples of linear or branched C ₁ -C ₆ alkyl (meth)acrylate monomers are methyl methacrylate (MMA), methyl and ethyl acrylate, propyl methacrylate, butyl methacrylate (BMA) and butyl acrylate (BA), n-butyl methacrylate (BMA), isobutyl methacrylate (IBMA), hexyl methacrylate and cyclohexyl methacrylate, cyclohexyl acrylate.

Examples of C ₇ -C ₃₀ alkyl (meth)acrylates are 2-butyloctyl (meth)acrylate, 2-hexyloctyl (meth)acrylate, decyl (meth)acrylate, 2-butyldecyl (meth)acrylate, octadecyl methacrylate (stearyl methacrylate (also called SMA), 2-hexyldecyl (meth)acrylate, 2-octyldecyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyl Dodecyl (meth)acrylate, 2-hexyldodecyl (meth)acrylate, 2-octyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, 2-decyltetra Decyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, 2-dodecylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl ( meth)acrylate, 4-tert-butyl octadecyl (meth)acrylate, 5-ethyl octadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, 2-decyl octadecyl (meth)acrylate, 2- Tetradecyl octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, cetyl eicosyl (meth)acrylate, stearyl eicosyl (meth)acrylate, docosyl (meth)acrylate, eicosyl tetratriacontyl (meth)acrylate ) acrylate, 2-decyl-tetradecyl (meth)acrylate, 2-decyl octadecyl (meth)acrylate, 2-dodecyl-1-hexadecyl (meth)acrylate, 1,2-octyl-1-dodecyl (meth)acrylate, 2- Tetradecyl octadecyl (meth)acrylate, 1,2-tetradecyl-octadecyl (meth)acrylate and 2-hexadecyl-eicosyl (meth)acrylate, n-tetracosyl (meth)acrylate, n-triacontyl (meth)acrylate and/or n- including, but not limited to, hexatriacontyl (meth)acrylate.

Preferably, the C ₁ -C ₄₀ alkyl (meth)acrylate monomer (b) is a linear, branched and cyclic C ₁ -C ₂₀ alkyl (meth)acrylate. More preferably, the monomer (b) is methyl (meth)acrylate, n-butyl (meth)acrylate, dodecyl (meth)acrylate (also called lauryl (meth)acrylate), pentadecyl (meth)acrylate, octadecyl methacrylate (stearyl (also called methacrylates), or mixtures thereof.

Monomer (c) :
According to the invention, said monomer (c) has a concentration of 500 to 10000 g/mol, preferably 1000 to 6000 g/mol, more preferably 1500 to 5500 g/mol, even more preferably 1800 to 5000 g/mol, most preferably 4500 g/mol. It is a polybutadiene-based macromonomer having a number average molecular weight (M _n ) of ~5000 g/mol, or a mixture thereof.

As used herein, the term "polybutadiene-based macromonomer(s)" refers to the reaction product of transesterification of an ester of (meth)acrylic acid with a hydroxylated hydrogenated polybutadiene; Refers to an ester of (meth)acrylic acid, which is any reaction product of the direct esterification of acrylic acid with hydroxylated hydrogenated polybutadiene.

In the following, the hydroxylated hydrogenated polybutadiene(s) of the present invention may also be referred to as MA ( M acro Alcohol ), and the polybutadiene macromonomer(s) of the present invention are: It is also called MM ( Macro Monomer ).

The content of monomer (c) in the monomer composition is 0 to 45% by weight, preferably 0 to 40% by weight, based on the total weight of the monomer composition.

As mentioned above, polyalkyl (meth)acrylates obtained from compositions containing said monomer (a), said monomer (b) and said monomer (c) are referred to as polybutadiene-containing PAMA.

The number average molecular weight (M _n ) of the macromonomer (c) is determined by gel permeation chromatography (GPC) using a polybutadiene calibration standard according to DIN 55672-1 using the following measurement conditions:
Eluent: Tetrahydrofuran (THF)
Operating temperature: 35℃
Columns: This column set consists of one precolumn (PSS-SDV, 10μ, 8x50mm), four PSS-SDV columns (SDV-LXL, SDV-LinL) with a size of 300x8mm and an average particle size of 10μm. , two columns SDV 100 Å (PSS Standards Service GmbH, Mainz, Germany)) and one solvent peak separation column (Shodex KF-800D) with a size of 8 × 100 mm, flow rate: 1 mL/min.
Injection volume: 100μL
Equipment: Agilent 1100 series consisting of autosampler, pump and column oven Detection equipment: Refractive index detector from the Agilent 1100 series.

The term "hydroxylated hydrogenated polybutadiene" as used herein refers to hydrogenated polybutadiene containing one or more hydroxyl groups. Said hydroxylated hydrogenated polybutadiene may further contain additional structural units, such as polyether groups derived from the addition of an alkylene oxide to the polybutadiene or maleic anhydride groups derived from the addition of maleic anhydride to the polybutadiene. It may be included. These additional structural units may be introduced into the polybutadiene when it is functionalized with hydroxyl groups.

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

These monohydroxylated hydrogenated polybutadienes can be produced by first converting butadiene monomer to polybutadiene by anionic polymerization. Hydroxy-functionalized polybutadiene can then be produced by reaction of the polybutadiene monomers with alkylene oxides, such as ethylene oxide or propylene oxide. The polybutadiene can also be reacted with more than one alkylene oxide unit to yield a polyether-polybutadiene block copolymer having terminal hydroxyl groups. The hydroxylated polybutadiene described above can be hydrogenated in the presence of a suitable transition metal catalyst.

These monohydroxylated hydrogenated polybutadienes are the products obtained by hydroboration of (co)polymers with terminal double bonds (as described, for example, in U.S. Pat. No. 4,316,973), with amino alcohols. , maleic anhydride-ene-amino alcohol adduct obtained by ene reaction of a (co)polymer with terminal double bonds with maleic anhydride, and hydroformylation of the (co)polymer with terminal double bonds, followed by hydrogenation. It is also possible to select from the products obtained by chemical reaction (for example, those described in JP-A-63-175096).

Preferably, the hydroxylated hydrogenated polybutadiene as starting material for monomer (c) has a hydrogenation level of at least 99%. An alternative measure of hydrogenation level that can be determined for the polymers of the invention is the iodine number. The iodine number refers to the number of grams of iodine that can be added to 100 g of polymer. Preferably, the polymers of the invention have an iodine value of 5 g iodine or less per 100 g of polymer. The iodine value is determined according to DIN 53241-1:1995-05 by the Wyss method.

Preferred hydroxylated hydrogenated polybutadienes are obtainable according to GB 2270317.

As mentioned above, macromonomers (c) for use according to the invention can be prepared by transesterification of alkyl (meth)acrylates. Reaction of the alkyl (meth)acrylate with the hydroxylated hydrogenated polybutadiene forms the ester of the invention. Preference is given to using methyl (meth)acrylate or ethyl (meth)acrylate as reactant.

This transesterification is widely known. For example, heterogeneous catalyst systems such as lithium hydroxide/calcium oxide mixtures (LiOH/CaO), pure lithium hydroxide (LiOH), lithium methoxide (LiOMe) or sodium methoxide (NaOMe) or It is possible to use 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 low molecular weight alcohol released is typically removed, for example by distillation.

Moreover, said macromonomer (c) can be prepared by direct esterification techniques, for example from (meth)acrylic acid or (meth)acrylic anhydride, preferably under acid catalysis with p-toluenesulfonic acid or methanesulfonic acid. , or from free methacrylic acid by the DCC method (dicyclohexylcarbodiimide).

Furthermore, this hydroxylated hydrogenated polybutadiene can be converted into an ester by reaction with an acid chloride, such as (meth)acryloyl chloride.

Preferably, in the above detailed preparation of the esters of the invention, polymerization inhibitors are used, such as 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl radical and/or hydroquinone monomethyl ether. Ru.

Monomer (d):
According to the invention, the monomer composition further comprises styrene and styrene derivatives having 8 to 17 carbon atoms, such as substituted styrenes having alkyl substituents in the side chain, such as α-methylstyrene and α-ethylstyrene. , substituted styrenes having alkyl substituents on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes, such as monochlorostyrene, dichlorostyrene, tribromostyrene and tetrabromostyrene, nitrostyrene, It may contain one or more monomers (d). A particularly preferred monomer (d) is styrene.

In a preferred embodiment of the invention, said monomer composition comprises 0 to 20% by weight, more preferably 5 to 15% by weight of one or more monomers (d), based on the total weight of said monomer composition.

Other monomers (e):
According to one aspect of the invention, the monomer composition comprises monomers (a), (b), optionally (c) and optionally may contain an additional monomer (e) in addition to (d).

Preferably, the amounts of monomers (a), (b), optionally (c) and/or optionally (d) in said monomer composition are based on the total amount of said monomers in said monomer composition. At least 80%, preferably totaling at least 90%, more preferably totaling at least 95% and most preferably totaling 98-100%.

Method for producing the polymer The polyalkyl (meth)acrylate according to the present invention can be produced by at least the following steps:
Obtained by a method comprising: (i) providing a monomer composition as defined above; and (ii) initiating radical polymerization in said monomer composition.

Standard free radical polymerization is described in detail in, inter alia, Ullmann's Encyclopedia of Industrial Chemistry, 6th edition. In general, polymerization initiators and optionally chain transfer agents may be used for this purpose.

The atom transfer radical polymerization (ATRP) method itself is well known. It is assumed that this is a "living" free radical polymerization, but is not intended to be limited by the above mechanistic explanation.

In these methods, a transition metal compound is reacted with a compound having a mobile atomic group. This involves the transfer of the mobile atomic group to the transition metal compound, with the result that the metal is oxidized. This reaction forms a free radical, which adds onto the ethylene group. However, the transfer of the atomic group to the transition metal compound is reversible, such that the atomic group is transferred back to the growing polymer chain, resulting in the formation of a controlled polymerization system. Accordingly, it is possible to control the formation of said polymer, its molecular weight and molecular weight distribution.

This reaction mode is described, for example, in J.-S. Wang, et al., J. Am. Chem. Soc, vol. 117, p. 5614-5615 (1995), Matyjaszewski, Macromolecules, vol. 28, p. 7901 -7910 (1995). Moreover, WO 96/30421, WO 97/47661, WO 97/18247, WO 98/40415 (WO 98/40415) and WO 99/10387 (WO 99/10387) disclose variations of the ATRP described above. Moreover, the polymers of the invention can also be obtained, for example, by the RAFT polymerization method. This method is described in detail in, for example, WO 98/01478 and WO 2004/083169.

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

Preferably, the monomer composition provided in step (i) is diluted by the addition of an oil, such as a conventional base oil, to provide the reaction mixture. The amount of said monomer composition, ie the total amount of monomers relative to the total weight of said reaction mixture, is preferably from 20 to 90% by weight, more preferably from 40 to 80% by weight, most preferably from 50 to 70% by weight.

Preferably, the oil used to dilute the monomer composition is an API Group I, II, III, IV or V oil, or a mixture thereof. Preferably, Group III oils or mixtures thereof are used to dilute the monomer composition.

Preferably step (ii) comprises the addition of a radical initiator.

Suitable radical initiators are, for example, azo initiators such as azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN) and 1,1-azobiscyclohexanecarboxylate. Nitriles, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl peroxy-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide , tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butyl Peroxy-3,5,5-trimethylhexanoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane , cumyl hydroperoxide, tert-butyl hydroperoxide and bis(4-tert-butylcyclohexyl) peroxydicarbonate.

Preferably, the radical initiator is 2,2'-azobis(2-methylbutyronitrile), 2,2-bis(tert-butylperoxy)butane, tert-butylperoxy 2-ethylhexanoate, 1, selected from the group consisting of 1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butylperoxybenzoate and tert-butylperoxy-3,5,5-trimethylhexanoate. Particularly preferred initiators are tert-butylperoxy 2-ethylhexanoate and 2,2-bis(tert-butylperoxy)butane.

Preferably, the total amount of radical initiator relative to the total weight of the monomer composition is from 0.01 to 7% by weight, more preferably from 0.05 to 6% by weight, most preferably from 0.1 to 5.5% by weight. be.

The entire amount of radical initiator may be added in a single step or in several steps during the course of the polymerization reaction. Preferably, the radical initiator is added in several steps. For example, a portion of the radical initiator may be added to initiate radical polymerization and a second portion of the radical initiator is added 0.5 to 3.5 hours after the first dose. You can.

Preferably step (ii) also includes the addition of a chain transfer agent. Suitable chain transfer agents are in particular oil-soluble mercaptans, such as n-dodecylmercaptan or 2-mercaptoethanol, or chain transfer agents from the class of terpenes, such as terpinolene. Particularly preferred is the addition of n-dodecylmercaptan.

Preferably, the total reaction time of the radical polymerization is from 2 to 10 hours, more preferably from 3 to 9 hours.

After completion of said radical polymerization, the obtained polymer is preferably further diluted with the above-mentioned oil to the desired viscosity. Preferably, the polymer is diluted to a concentration of 5-60%, more preferably 10-50%, most preferably 20-40% by weight of polymer.

Use of the Polymer According to the Invention According to the invention, the polyalkyl (meth)acrylate polymer of the invention described above is used for inhibiting or reducing copper corrosion of metals consisting of or containing copper. Fluids in direct contact with metal parts of electrical or mechanical equipment, such as lubricants, dielectric It can be used as a copper corrosion inhibiting additive for fluids, coolants or fuels or gear and axle fluids, electric vehicle transmission fluids and fluids for batteries or other electrical equipment systems.

In addition to inhibiting copper corrosion, the polyalkyl (meth)acrylates according to the invention have good solubility in various base oils and excellent viscosity index improving properties and in the same way as polyalkyl (meth)acrylates known from the prior art. It has properties of improving shear stability.

Accordingly, the polyalkyl (meth)acrylate polymers of the present invention have high solubility in base oils and are synthesized in base oils or base oil mixtures or mixed with one or more base oils. It can be used as a copper corrosion inhibitor that has a viscosity index improving effect and a shear stabilizing effect.

Moreover, it is found that the polyalkyl (meth)acrylate polymers of the present invention have superior dispersion ability and lower electrical conductivity compared to those described in the prior art.

Compositions Comprising Polyalkyl (meth)acrylates According to the Invention Compositions according to the invention include:
(A) one or more base oils, and (B) one or more polyalkyl (meth)acrylate polymers as described above, and within a temperature range of 130 to 240°C, preferably in a range of 30 to 200°C, and Preferably, it is used within the range of 150 to 200° C. to suppress, reduce or prevent copper corrosion of metal parts.

According to the present invention, the term "base oil" refers to base oil or fuel.

The concentration (also called treatment rate) of the polyalkyl (meth)acrylate according to the invention in said base oil is preferably from 0.1 to 99.8% by weight, more preferably from 0.1% to 99.8% by weight, based on the total weight of said composition. It can range within a wide range, from .5 to 99.5% by weight.

According to the invention, said composition may be an additive composition comprising a polyalkyl (meth)acrylate according to the invention and one or more base oils as diluent. The additive composition may be added, for example, as a copper corrosion inhibitor to lubricants, dielectric fluids, coolants, fuels or any other hydrocarbon-based fluid that comes into direct contact with metal parts.

When the composition of the present invention is used as an additive composition, the amount of said one or more base oils (component (A)) is each based on the total weight of said additive composition. , preferably 0.5 to 80% by weight, more preferably 20 to 80% by weight, and the amount of the polymer (component (B)) is preferably 20 to 99.5% by weight, more preferably 80 to 20% by weight. Weight%.

The compositions of the present invention may include lubricants, dielectric oils, coolants or It may also be fuel. The lubricant compositions may be used, for example, as transmission or engine oils, gear and axle fluids, electric vehicle transmission fluids and fluids for batteries or other electrical equipment systems. Generally, the composition of the invention as one of the fluids described above contains a lower amount of the polymer according to the invention compared to the additive composition described above.

When the composition of the invention is used as such a fluid, the amount of said base oil (component (A)) is preferably between 80 and 99.9%, respectively, based on the total weight of said composition. 9% by weight, more preferably 85-99.5% by weight, most preferably 90-99% by weight, and the amount of polymer (component (B)) is preferably 0.1-20% by weight of said polymer, More preferably 0.5 to 15% by weight, most preferably 1 to 10% by weight.

Preferably, the amounts of (A) and (B) add up to 95-100% by weight, based on the total weight of the composition.

The polyalkyl (meth)acrylates and compositions containing the polyalkyl (meth)acrylates of the present invention can be used in drive systems (e.g., manual transmission oils, differential gear oils, automatic transmission oils, belt-type continuously variable transmission oils, axle fluids). formulations, dual-clutch transmission fluids, and hybrid-specific transmission fluids), hydraulic fluids (e.g. mechanical fluids, power steering fluids, shock absorber fluids), engine oils (for gasoline engines) to cool and lubricate the E-drive. and diesel engines) and industrial oil formulations (e.g. for wind turbine applications) or as coolants and fuels.

Kinematic viscosity may be measured according to ASTM D445. Preferably, said kinematic viscosity is measured at temperatures of 100<0>C and 40<0>C.

Shear resistance is preferably evaluated by measuring the properties of the lubricant before and after subjecting it to shear according to JASO M347. Preferably, shear is measured using an ultrasonic shear stability tester according to JASO M347-4.5.1 (1 hour method).

The base oils (A) that may be used in the compositions include natural and synthetic oils, oils derived from hydrocracked, hydrogenated, and hydrofinished, unrefined, refined, recycled oils or mixtures thereof. include.

Said base oil may also be defined as specified by the American Petroleum Institute (API) (Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, April 2008 Edition, Sec. 1.3, subheading 1.3. “Base Stock Categories”).

API currently defines five groups of lubricant base stocks (API 1509, Annex E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, September 2011). Groups I, II and III are mineral oils classified by the amount of saturates and sulfur they contain and by their viscosity index, Group IV are polyalphaolefins, and Group V are e.g. This includes everything else, including oil. Table 1 below describes these API classifications.

Table 1 :

The kinematic viscosity at 100° C. (KV ₁₀₀ ) of suitable base oils used to prepare the lubricant compositions according to the invention is preferably in the range of 1 mm ² /s to 10 mm ² /s according to ASTM D445. , more preferably in the range of 1 mm ² /s to 8 mm ² /s, even more preferably in the range of 1 mm ² /s to 5 mm ² /s.

Further base oils that can be used according to the invention are Group II-III Fischer-Tropsch derived base oils.
Fischer-Tropsch derived base oils are known in the art. The term "Fischer-Tropsch derived" means that the base oil is or is derived from a synthetic product of the Fischer-Tropsch process. Fischer-Tropsch derived base oils are sometimes referred to as GTL (gas to liquid) base oils. Suitable Fischer-Tropsch derived base oils which can be advantageously used as base oils in the lubricating compositions of the present invention are described, for example, in EP 0 776 959, EP 0 668 342. International Publication No. 97/21788 (WO97/21788), International Publication No. 00/15736 (WO00/15736), International Publication No. 00/14188 (WO00/14188), International Publication No. 00/14187 No. (WO00/14187), International Publication No. 00/14183 (WO00/14183), International Publication No. 00/14179 (WO00/14179), International Publication No. 00/08115 (WO00/08115), International Publication No. 99 /41332 (WO99/41332), European Patent Application Publication No. 1029029 (EP1029029), International Publication No. 01/18156 (WO01/18156), International Publication No. 01/57166 (WO01/57166) and International Publication It is disclosed in No. 2013/189951 (WO2013/189951).

Particularly for transmission oil formulations, API Group III base oils and mixtures of different Group III oils are used. In a preferred embodiment, the one or more base oils (A) are an API Group III base oil or a mixture of API Group III base oils.

The composition preferably has a viscosity index of greater than 150, more preferably greater than 180. The viscosity index may be measured according to ASTM D2270.

Additive :
The compositions according to the invention contain friction modifiers, dispersants, defoamers, detergents, antioxidants, pour point depressants, anti-wear additives, extreme pressure additives, anti-corrosion additives other than copper corrosion inhibitors. , dyes and mixtures thereof.

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

Dispersants (including borated dispersants) are preferably used in amounts of 0 to 5% by weight, based on the total weight of the lubricant composition.

Suitable defoamers are silicone oils, fluorosilicone oils and fluoroalkyl ethers.

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

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, in particular, calcium, magnesium and barium. These compounds may preferably be used in neutral or overbased form.

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

Suitable antioxidants include, for example, phenolic antioxidants and aminic antioxidants.

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

The amine antioxidants include, for example, monoalkyldiphenylamine, such as monooctyldiphenylamine, monononyldiphenylamine; dialkyldiphenylamine, such as 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine. , 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine; polyalkyldiphenylamine, such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine; naphthylamines , specifically α-naphthylamine, phenyl-α-naphthylamine and further alkyl-substituted phenyl-α-naphthylamines, such as butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α - including naphthylamine, octylphenyl-α-naphthylamine, and nonylphenyl-α-naphthylamine. Among these, diphenylamines are more preferred than naphthylamines from the viewpoint of their antioxidant effect.

Suitable antioxidants are furthermore compounds containing sulfur and phosphorus, such as metal dithiophosphates, such as zinc dithiophosphate (ZnDTP), "OOS triesters" = dithiophosphoric acids, and olefins, cyclopentadiene, norbornadiene, α-pinene. , reaction products with activated double bonds from polybutenes, acrylic esters, maleic esters (ashless on combustion); organic sulfur compounds such as dialkyl sulfides, diaryl sulfides, polysulfides, modified thiols, thiophene derivatives, xanthates, thioglycols, thioaldehydes, sulfur-containing carboxylic acids; heterocyclic sulfur/nitrogen compounds, especially dialkyldimercaptothiadiazole, 2-mercaptobenzimidazole; zinc bis(dialkyldithiocarbamates) and methylenebis(dialkyldithiocarbamates); organic phosphorus compounds , for example triaryls and trialkyl phosphites; organocopper compounds and overbased calcium and magnesium-based phenoxides and salicylates.

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

The pour point depressants include ethylene-vinyl acetate copolymers, chlorinated paraffin-naphthalene condensates, chlorinated paraffin-phenol condensates, polyalkyl (meth)acrylates, and polyalkylstyrenes. Preference is given to polyalkyl (meth)methacrylates with a weight average molecular weight of 5000 to 200000 g/mol.

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

Preferred antiwear and extreme pressure additives are sulfur-containing compounds such as zinc dithiophosphate, zinc di-C _3-12 -alkyldithiophosphate (ZnDTP), zinc phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate. , disulfides, sulfurized olefins, sulfurized fats and oils, sulfurized esters, thiocarbonates, thiocarbamates, polysulfides, phosphorus-containing compounds such as phosphites, phosphates such as trialkyl phosphates, triaryl phosphates such as tricresyl phosphate, amine-neutralized monoalkyl and dialkyl phosphates, ethoxylated monoalkyl and dialkyl phosphates, phosphonates, phosphines, amine or metal salts of their compounds; sulfur- and phosphorus-containing antiwear agents such as thiophosphites, thiophosphates, thiophosphonates, amines of their compounds Contains salts or metal salts.

The antiwear agent is present in an amount of 0 to 3% by weight, preferably 0.1 to 1.5%, more preferably 0.5 to 0.9% by weight, based on the total weight of the composition. It's okay to stay.

Preferred friction modifiers are mechanically active compounds, such as molybdenum disulfide, graphite (including graphite fluoride), poly(trifluoroethylene), polyamides, polyimides; compounds that form adsorption layers, such as long-chain carboxylic acids. , fatty acid esters, ethers, alcohols, amines, amides, imides; compounds forming layers by tribochemical reactions, such as saturated fatty acids, phosphoric and thiophosphoric acid esters, xanthogenates, sulfurized fatty acids; compounds forming polymer-like layers, For example, ethoxylated dicarboxylic acid partial esters, dialkyl phthalates, methacrylates, unsaturated fatty acids, sulfurized olefins and organometallic compounds, such as molybdenum compounds (molybdenum dithiophosphate and molybdenum dithiocarbamate MoDTC) and their combinations with ZnDTP, copper-containing organic compounds. It may be included.
Some of the compounds listed above may fulfill multiple functions. For example, ZnDTP is primarily an antiwear additive and an extreme pressure additive, but also has the characteristics of an antioxidant and corrosion inhibitor (here: metal passivator/deactivator).

The additives detailed above can be found in, inter alia, T. Mang, W. Dresel (eds.): “Lubricants and Lubrication”, Wiley-VCH, Weinheim 2001; R. M. Mortier, S. T. Orszulik (eds.): “Chemistry and Technology of Lubricants”.

Preferably, the total concentration of said one or more additives is up to 20% by weight, more preferably from 0.05% to 15% by weight, more preferably 5% by weight, based on the total weight of said composition. ~15% by weight.

Preferably, the amounts of the polymer according to the invention, said base oil or fuel and optionally one or more additives total from 95 to 100% by weight, preferably in total, based on the total weight of said composition. It becomes 100% by weight.

Method of inhibiting or reducing copper corrosion using compositions according to the invention In a further aspect, the present invention provides a method for inhibiting or reducing copper corrosion using compositions according to the invention. It also relates to a method for inhibiting or reducing copper corrosion in at least one metal component consisting of or containing copper, using the composition defined in detail above.

Preferably, said metal part is a part of a vehicle powertrain, more preferably an engine, electric motor, battery, transmission, shaft or gear.

In this method, the copper corrosion is measured according to ASTM D130, Copper Corrosion Test, as described in detail in the experimental section below.

EXPERIMENTAL PART The invention will be further explained in detail below with reference to examples and comparative examples, which are in no way intended to limit the scope of the invention.

Abbreviation Biodiesel Biodiesel fuel having a KV ₁₀₀ (ASTM D-445) of 1.8 cSt (see Table 8)
C ₁ AMA C ₁ -alkyl methacrylate (methyl methacrylate, MMA)
C ₄ AMA C ₄ -alkyl methacrylate (n-butyl methacrylate, BMA)
C _12-14 AMA Linear C _12-14 -alkyl methacrylate (lauryl methacrylate, LMA)
C _12-15 AMA Branched C _12-15 -alkyl methacrylate (lauryl isopentadecyl _methacrylate , LIMA)
C _12-15 AMA Branched C _12-15 -alkyl methacrylate (dodecyl pentadecyl methacrylate, DPMA)
C _16-20 AMA C _16-20 -alkyl methacrylate (stearyl methacrylate, SMA)
CTA Chain transfer agent DEHF Diethylhexyl fumarate DMAEMA Dimethylaminoethyl methacrylate DMAPMA N-3-dimethylaminopropyl methacrylamide EHA Ethylhexyl acrylate f _Branching degree [mol%]
GTL ₄ gas liquefaction _technology , _Risella Kinematic viscosity MA-1 determined at 100 °C according to D-445 or ISO 3104 Macroalcohol (hydroxylated hydrogenated polybutadiene M _n =4900 g/mol)
MM-1 Macromonomer of MA-1 with methacrylate functional group M _n number average molecular weight M _w weight average molecular weight
NB3043 ^Nexbase® 3043, Group III base oil NVP N-vinylpyrrolidone from Neste with a KV ₄₀ (ASTM D-445) of 20 cSt
Oil I-12A Industrial Group I base oil PAO from Gazprom Neft with KV ₄₀ of 14 cSt (ASTM D-445) Chevron Phillips Oil Additives Synfluid PAO 4 synthetic polyalphaolefin, KV ₄₀ of 16.8 cSt (ASTM D-445) ) Group IV base oil PDI Molecular weight distribution calculated by polydispersity index, M _w /M _n Styrene.

Synthesis of Hydroxylated Hydrogenated Polybutadiene (Macroalcohol) MA-1 The macroalcohol was synthesized by anionic polymerization of 1,3-butadiene using butyllithium at 20-45°C. When the desired degree of polymerization was reached, the reaction was stopped by adding propylene oxide and the lithium was removed by precipitation with methanol. Subsequently, the polymer was hydrogenated under a hydrogen atmosphere in the presence of a noble metal catalyst at a maximum of 140° C. and a pressure of 200 bar. After the hydrogenation was completed, the noble metal catalyst was removed and the organic solvent was removed under reduced pressure to obtain 100% macroalcohol MA-1. Table 2 summarizes the characteristic data of MA-1:
Table 2 : Characteristic data of the macroalcohols used

Synthesis of macromonomer MM-1 Saber stirrer, air inlet tube, thermocouple with controller, heating mantle, column with irregular packing of 3 mm wire spirals, vapor distributor, top thermometer, reflux condenser and In a 2L stirrer equipped with a cooling plate, 1000 g of the above macroalcohol are dissolved in methyl methacrylate (MMA) by stirring at 60°C. Added to the solution are 20 ppm of 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 200 ppm of hydroquinone monomethyl ether. After heating to MMA reflux (bottom temperature approximately 110° C.) while passing air for stabilization, approximately 20 mL of MMA are distilled off for azeotropic drying. After cooling to 95° C., LiOCH ₃ is added and the mixture is heated to reflux. After about 1 hour of reaction time, the top temperature dropped to about 64° C. due to methanol formation. The methanol/MMA azeotrope formed is constantly distilled off until a constant top temperature of about 100° C. is reestablished. At this temperature, the mixture is allowed to react for a further hour. Most of the MMA is removed under reduced pressure for further work-up. Insoluble catalyst residues are removed by pressure filtration (Seitz T1000 depth filter). Table 3 summarizes the amounts of MMA and LiOCH ₃ used in the synthesis of macromonomer MM-1.

Table 3 : Macroalcohol, MMA and catalyst amounts for transesterification of the macromonomers

Preparation of Polymers A polybutadiene-containing PAMA (P1) according to the invention and some PAMA polymers (P2-P5) and some comparative polymers (P6-P8) were prepared according to the manufacturing procedure described below. For examples P1, P2, P3, P4, P5, P6, P7 and P8, the monomer components add up to 100%. The amounts of initiator and chain transfer agent (CTA) are given relative to the total amount of monomer. Tables 4 and 5 below list the monomer compositions and reactants for making the inventive polymers P1, P2, P3, P4, P5 and the comparative polymers P6, P7 and P8, respectively, and their final properties. shows.

The weight-average and number-average molecular weights of the polymers were determined by gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) calibration standards for PAMA polymers and polystyrene (PS) for polybutadiene-containing PAMA polymers, as described above. Measured using a calibration standard. In both cases, tetrahydrofuran (THF) containing 0.02M 2-diethylaminoethylamine is used as eluent.

Polymers P1 to P5 of the present invention
Example Polymer 1 (P1) : Preparation of an amine- and macromonomer-containing copolymer according to the invention
Nexbase 3020 85 g, Berylane 230SPP 85 g, macromonomer MM-1 98 g, butyl methacrylate 107 g, styrene 28 g, lauryl methacrylate 12.5 g, dimethylaminopropyl methacrylamide 8.6 g, methyl methacrylate 0.5 g and n-dodecyl mercaptan 0.1 g was placed into a 2 liter four-necked round bottom flask. The reaction mixture was stirred using a C-type stir bar, inert with nitrogen, and heated to 115°C. Once the reaction mixture reached the set point temperature, 0.9 g of tert-butyl-2-ethyl peroxyhexanoate was fed into the reactor over a period of 3 hours. 0.5 g of 2,2-di-(tert-butylperoxy)butane was added within 30 minutes and 3 hours after the previous feed. The reaction mixture was stirred for 1 hour and then an additional 175 g of Nexbase 3020 was added to the reactor and mixed for 1 hour. The polymer obtained has a weight average molecular weight (M _w ) of 238 000 g/mol (determined using a PS standard).

Example Polymer 2 (P2) : Preparation of an amine-containing copolymer according to the invention Polymer 2 was prepared in the same way as Polymer 1. Starting materials for P2 are shown in Table 4. The polymerization setpoint temperature is in this case 80°C instead of 90 and 100°C. The final polymer obtained has a weight average molecular weight (M _w ) of 30 000 g/mol (determined using a PMMA standard).

Example Polymer 3 (P3) : Preparation of an amine-containing copolymer according to the invention Polymer 3 was prepared in the same way as Polymer 1. Starting materials for P3 are shown in Table 4. The final polymer obtained has a weight average molecular weight (M _w ) of 15500 g/mol (determined using a PMMA standard).

Example Polymer 4 (P4) : Preparation of an amine-containing copolymer according to the invention Polymer 4 was prepared in the same way as Polymer 1. Starting materials for P4 are shown in Table 4. The final polymer obtained has a weight average molecular weight (M _w ) of 47,000 g/mol (determined using a PMMA standard).

Example Polymer 5 (P5) : Preparation of an amine-containing copolymer according to the invention Polymer 5 was prepared in the same way as Polymer 1. Starting materials for P5 are shown in Table 4. The final polymer obtained has a weight average molecular weight (M _w ) of 43000 g/mol (determined using a PMMA standard).

Comparison polymer:
Comparative example polymer 6 (P6)
Polymer 6 was prepared in the same manner as Polymer 1. Starting materials for P6 are shown in Table 5. The final polymer obtained has a weight average molecular weight (M _w ) of 182000 g/mol (measured using the same GPC method as macromonomer (c) as above, but using a PMMA standard) .

Comparative example polymer 7 (P7)
Polymer 7 was prepared in the same manner as Polymer 1. The starting materials for P7 are shown in Table 5. The final polymer obtained has a weight average molecular weight (M _w ) of 13900 g/mol (measured using the same GPC method as macromonomer (c) as above, but using the PMMA standard) .

Comparative example polymer 8 (P8)
1.785 g of DBPO (0.3% by weight relative to the monomers in the feed) dissolved in 581.7 g of ethylhexyl acrylate (EHA) and 13.3 g of diethylhexyl fumarate (DEHF) were added to 105.0 g of 1-tetradecene. was slowly fed under nitrogen at 160° C. for 3 hours. After stirring for another hour, the resulting colorless and clear polymer was cooled and used without further purification. The final polymer obtained has a weight average molecular weight (M _w ) of 20300 g/mol (determined using a PMMA standard).

For the examples P1, P2, P3, P4, P5, P6, P7 and P8, the monomer components add up to 100%. The amounts of initiator and chain transfer agent (CTA) are given relative to the total amount of monomer. Tables 4 and 5 below show the monomer compositions and reactants for making the polymers P1, P2, P3, P4, P5, P6, P7 and P8 and their final properties.

Copper plate test: Experimental details according to ASTM D130 The above polymers P1, P2, P3, P4, P5, P6, P7 and P8 were subjected to a copper plate test (copper plate test conducted at 180°C for 3 hours) according to ASTM D130. To do this, it was dissolved in base oil.

A freshly polished copper plate was immersed in 35 mL of a sample oil of the invention or a comparative sample oil in a glass beaker with a gas permeable stopper, and the samples were prepared as shown in Tables 7, 9 and 10 below. Heating under temperature conditions and over a length of time. At the end of the heating period, the copper plate was removed, cleaned with petroleum ether, and its color and discoloration level was evaluated against the ASTM Copper Plate Corrosion Standard. The classification according to ASTM D130 for the evaluation of said corrosion is defined in Table 6.

ASTM D130銅板腐食標準は、前記の変色の状態に示す特徴を持つ板で作られている。 Table 6 : Classification of copper plates according to ASTM D130

The ASTM D130 Copper Plate Corrosion Standard is made of plates with the characteristics shown in the discoloration conditions described above.

Table 7 : Performance of state of the art corrosion inhibitors and comparative examples P6, P7 and P8 in API Group III base oils

As shown in Table 7 above, the use of conventional corrosion inhibitors, such as dithiothiazole derivatives as disclosed in US Pat. No. 4,012,408 A1, is probably ineffective at high temperatures. This is because the copper corrosion inhibitor is not stable at high temperatures (dark coloration).

Comparative polymers P6 and P7 and comparative polymer P8, which are devoid of any nitrogen functionality, provide no improvement in copper corrosion inhibition or even lead to worse results when used at high temperatures.

Table 8 : Fatty acid distribution of biodiesel used in the tests in Table 9

The biodiesel in Table 8 is a fuel with a KV ₁₀₀ (ASTM D-445) of 1.8 cSt.

Table 9 : Performance of copper corrosion inhibitor according to the invention in biodiesel fuel

Polymer P3 according to the invention was tested as a corrosion inhibitor additive in biodiesel fuel with the results of a copper plate test according to ASTM D130 carried out at 180° C. for 3 hours. As shown in Table 9, the polymers of the present invention provide significant improvement against copper corrosion in fuels.

Table 10, shown below, shows the performance of the polymers according to the invention as corrosion inhibitor additives in base oils, together with the results of copper plate tests according to ASTM D130 carried out at 180° C. for 3 hours at different treatment rates.

Table 10 : Performance of polymers according to the invention as corrosion inhibitor additives in base oils

GTL 4, PAO, Oil I-12A and NB 3043 are base oils. Compared to the results obtained from the sample oils without any polymers of the invention (rating: 2c), the sample oils treated with polymers P1 to P5 according to the invention have a much better rating for the copper plate test. As confirmed by the test results, it clearly shows remarkable effectiveness in inhibiting or reducing copper corrosion. Accordingly, the polymers of the present invention have been shown to be effective copper corrosion inhibitors for inhibiting or preventing copper corrosion in metal parts.

Claims (15)

A composition for preventing or inhibiting copper corrosion within a temperature range of 130-240°C, comprising:
Based on the total weight of monomers in the (A) one or more base oils and (B) monomer composition:
(a) 1 to 35% by weight, preferably 1.5 to 30% by weight, more preferably 2 to 30% by weight of one or more nitrogen-containing ethylenically unsaturated monomers;
(b) 40-99% by weight, preferably 45-98% by weight of one or more monomers selected from the group consisting of linear, branched and cyclic C ₁ -C ₄₀ alkyl (meth)acrylates, and ( c) 0-45% by weight, preferably 0-40% by weight of one or more polybutadiene macromonomers having a number average molecular weight of 500-10000 g/mol
said composition comprising one or more polyalkyl (meth)acrylates obtainable by radical polymerization of a monomer composition comprising. The one or more nitrogen-containing ethylenically unsaturated monomers (a) as described above are:
(a1) aminoalkyl (meth)acrylate and aminoalkyl (meth)acrylamide,
(a2) (meth)acrylates derived from nitrogen-functionalized (meth)acrylic acid derivatives and ketones having at least one cyano or nitrile group;
(a3) a nitrogen-functionalized (meth)acrylate having at least one further carbonyl group;
(a4) nitrogen-functionalized cyclic (meth)acrylate,
The composition of claim 1 selected from the group consisting of (a5) nitrogen-functionalized cyclic vinyl compounds. The one or more nitrogen-containing ethylenically unsaturated monomers (a) as described above are:
(a1) N-(3-dimethylaminopropyl)methacrylamide, 3-diethylaminopentyl (meth)acrylate, 3-dimethylaminoethyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylate, 3-dibutyl-aminohexa Decyl (meth)acrylate,
(a2) N-(methacryloyloxyethyl)diisobutylketimine, N-(methacryloyloxyethyl)dihexadecyl-ketimine, (meth)acryloylamide acetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethyl(meth)acrylate,
(a3) N-(methacryloyloxy)-formamide, N-methacryloyl-2-pyrrolidinone, N-(2-methacryloyloxyethyl)-2-pyrrolidinone, N-(3-methacryloyloxy-propyl)-2-pyrrolidinone, N -(2-methacryloyloxypentadecyl)-2-pyrrolidinone, N-(3-methacryloyloxyheptadecyl)-2-pyrrolidinone,
(a4) 2-(1-imidazolyl)ethyl (meth)acrylate, 2-(4-morpholinyl)ethyl (meth)acrylate, oxazolidinylethyl (meth)acrylate and N-methacryloylmorpholine,
(a5) 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9- Vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinyl The composition according to claim 1 or 2, selected from the group consisting of caprolactam, N-vinylbutyrolactam. Claim 3 wherein said one or more nitrogen-containing ethylenically unsaturated monomers are selected from the group consisting of N-3-dimethylaminopropyl methacrylamide, N-vinylpyrrolidone, dimethylaminoethyl methacrylate or mixtures thereof. Compositions as described. The monomer composition is based on the total weight of monomers in the monomer composition:
(a) 1.5 to 30% by weight, preferably 2 to 30% by weight of one or more nitrogen-containing ethylenically unsaturated monomers;
(b) 45-98% by weight of one or more monomers selected from the group consisting of linear, branched and cyclic C ₁ -C ₄₀ alkyl (meth)acrylates, and (c) one or more polybutadiene systems. Macromonomer 0-40% by weight
5. A composition according to any one of claims 1 to 4, comprising: The monomer composition further comprises, based on the total weight of monomers in the monomer composition:
(d) 0 to 20% by weight, preferably 5 to 15% by weight of styrene or styrene derivatives having 8 to 17 carbon atoms;
A composition according to any one of claims 1 to 5, comprising: From claim 1, wherein the one or more polyalkyl (meth)acrylates have a measured weight average molecular weight of from 5000 to 300 000 g/mol, preferably from 8000 to 280 000 g/mol, more preferably from 10 000 to 250 000 g/mol. 6. The composition according to any one of items 6 to 6. The one or more polybutadiene macromonomers (c) have a number average molecular weight of 1000 to 6000 g/mol, preferably 1500 to 5500 g/mol, together with one or more (meth)acrylic acid or (meth)acrylate. 8. Composition according to any one of claims 1 to 7, which is an ester with one or more hydroxylated hydrogenated polybutadienes. The content of the one or more polyalkyl (meth)acrylates (B) is from 20 to 99.5% by weight, preferably from 20 to 80% by weight, based on the total weight of the composition. 9. The composition according to any one of 1 to 8. The content of the one or more polyalkyl (meth)acrylates (B) is from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 0.5 to 15% by weight, based on the total weight of the composition. 9. A composition according to any one of claims 1 to 8, wherein: 1 to 10% by weight. 10. A composition according to claim 9 as an additive to a lubricant, dielectric fluid, coolant fluid or fuel. 11. A composition according to claim 10 as a lubricant, dielectric fluid, coolant fluid or fuel. in a temperature range of 130 to 240°C, preferably 130 to 200°C, more preferably 150 to 200°C, in a manner that inhibits or reduces copper corrosion of at least one metal component consisting of or containing copper. 13. A method according to claim 1, wherein said method uses a composition as defined in any one of claims 1 to 12. 14. The method according to claim 13, wherein the metal part is a part of a vehicle powertrain, preferably an engine, electric motor, battery, transmission, shaft or gear part. 15. A method according to claim 13 or 14, wherein the copper corrosion is measured according to the ASTM D130 copper corrosion test.