Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
  • C10M145/14—Acrylate; Methacrylate
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid

Definitions

• the invention relates to improved additives for Lubricating oils, in particular for gear oils based on Polymers of long-chain alkyl esters are more polymerizable Acids selected from the group consisting of (Meth) acrylic acid esters, fumaric acid esters, maleic acid esters, and copolymers of the same with each other and with other comonomers.
• Oil-soluble polymers have been used as lubricant additives for many decades. There was particular interest in influencing the temperature-viscosity behavior of lubricants, especially motor oils. The empirically based so-called viscosity index counts as a measure (see Kirk-Othmer, 3rd Ed Ed. 14 , 477-526, J. Wiley 1981). As so-called viscosity index improvers (VI improvers), in addition to polyolefins, in particular olefin copolymers (so-called OCPs), polymers from the higher esters of (meth) acrylic acid are advantageously used (so-called PAMA), which, through appropriate functionalization, also have dispersing or Detergent effect can be conferred. (See H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylitatien, pp. 314 - 316, Springer-Verlag 1968).
• the gear oil components described are typically relatively low molecular weight polyalkyl (meth) acrylates. But there are also (meth) acrylate homo- and co-oligomers in question (cf. DE-A 40 25 494).
• U.S. Patent 5,112,509 (Texaco) describes a copolymer of methyl methacrylate and Lauryl methacrylate and the process for its preparation by radical Copolymerization started by azobis (isobutyronitrile) as a catalyst.
• the Copolymers are used as VI-improving additives for hydraulic oils and lubricating oils used.
• the transmission oil In manual gearboxes, the transmission oil must also ensure that the synchronizing systems, for the function of which the friction coefficients of the lubricant are of the utmost importance, are still perfectly functional even after more than 100,000 switching operations between two gears, i.e. without scratching, noises or increased effort.
• oils with a high polymer content have so far reduced the lifespan of synchronous systems to such an extent that gear oils containing high shear strength VI improvers could not generally be introduced. Since the production, handling, etc. of the polymers used had been done legally, there seemed to be no way to solve these problems, for example by improving the product quality.
• polymer additives according to claim 1 of the present invention are used.
• the polymer additives to be used according to the invention are produced in a manner known per se by free-radically initiated polymerization of (meth) acrylate monomers.
• the radical formation is triggered, for example, by the decay of thermolabile radical initiators (cf. J. Brandrup, EH Immergut, Polymer Handbook, 3rd. Ed. Chapter III, pp. 1-65, J. Wiley 1989; HF Mark et al., Encyclopedia of Polymer Science & Engineering, 2nd.Ed.Vol. 11 , 2 - 21, J. Wiley 1988; H.
• Easily separable splitting pieces are to be understood in particular as volatile, that is to say those which evaporate or sublime, preferably at least at the polymerization temperature.
• the upper limit can be a boiling point of the fission products of 130 degrees C at 10 mm pressure.
• a selection criterion for the selection of initiators RI without excessively polar cleavage products can be, for example, that no acyl groups are formed during the decomposition or no groups that convert into acid groups under subsequent conditions (moisture and catalytic influences).
• the choice of the initiators RI to be used according to the invention based on the criteria ⁇ ) formation of easily separable fragments or / and ⁇ ) absence of strongly polar cleavage products is simple for the person skilled in the art: first of all, the decomposition of the initiators known per se is both group-wise and individual in the relevant literature on the other hand, analytical aids, in particular gas chromatography and mass spectrometry, are available both individually and in combination, which allow them to be checked without any particular effort.
• gas chromatography enables the detection of vaporizable substances or their fission products. Under the conditions of mass spectrometry, substances are broken down at certain points. For initiators, these "predetermined breaking points" are representative fragments of the radicals that form.
• the additives - polymers and oligomers - according to the present invention are selected from the group of esters with long-chain alkyl radicals, the alkyl radicals usually in the range 6 to 42 carbon atoms, preferably 8 to 28 carbon atoms in the alkyl radical or copolymers formed from the monomers of the olefin group with 2 to 16 carbon atoms, the vinyl ester of fatty acids with 1 to 12 carbon atoms in the acid residue.
• the composition is appropriately adjusted so that the polymers or oligomers / cooligomers are oil-soluble.
• the polymers or oligomers / cooligomers are preferably composed of monomers selected from the group consisting of the compounds of the formula IV wherein R 5 represents an optionally branched alkyl radical having 8 to 24 carbon atoms and R represents hydrogen or methyl and / or from the compounds of the formula V.
• esters of the formula IV with various long-chain alkyl radicals is particularly preferred.
• the preferred group of additives includes (co) oligomers which are composed of 20 to 100% by weight of the monomers of the formula IV and, if appropriate, VI (cf. DE-A 40 25 493, DE-A 40 25 494).
• particular interest may be (co) oligomers from 0 to 80% by weight, preferably 10 to 60, in particular 10 to 40% by weight of the monomers of the formula VI and 20 to 100, preferably 40 to Claim 90 wt .-% of the monomers of formula IV.
• Examples include the monomers of the formula IV:
• alkyl methacrylates with ⁇ C 10 in the alkyl radical with a higher iso content examples include C 12 -C 15 alkyl esters of methacrylic acid with about 60-90% iso content and isodecyl methacrylate.
• alkenes such as vinylcyclohexane, 3,3-dimethylbutene-1, 3-methylbutene-1, diisobutylene-4-methylpentene-1 or the like.
• alkenes-1 with 10 to 32 carbon atoms which are obtained in the polymerization of ethylene, propylene or mixtures thereof, these materials in turn being obtained from hydrocracked materials.
• the embodiment in which the monomer of the formula VI in the cooligomers is 1-decene or dodecene or tetradecene is particularly preferred.
• Cooligomers based on ⁇ -olefin / long-chain alkyl (meth) acrylic acid esters can be represented, for example, as follows:
• the ⁇ -olefin, for example 1-decene is placed in a suitable, heatable reaction vessel and heated, preferably to above 100 ° C., as a guide be called about 140 degrees C - and the alkyl methacrylate component - usually present as a mixture of different long-chain esters - added over a few hours.
• initiator RI is added during the entire polymerization period, except for the last, approximately one-hour, section.
• the peroxidiketals described, for example, are preferred as initiators in the present case. Any fragments of initiator still present and any residual monomers can be removed, for example, by distillation, preferably in a (weak) vacuum.
• long-chain polyalkyl (meth) acrylates PAMA
• PAMA polyalkyl (meth) acrylates
• the mixture is heated, for example, to over 100 ° C. and the long-chain alkyl (meth) acrylates are metered in over a certain period of time, 4 hours as a reference.
• chain regulators known per se are used, as a reference point 0.05 to 3, a maximum of 2.5 to 3% by weight based on the monomers (typical value 0.5% by weight regulator) called, in particular mercapto controller and initiator RI, as a guide again max. 2.5% by weight based on the monomers (typical values 0.5-1.7% RI) based on the monomers, added.
• the molecular weight M w of the products formed is in the range 500-30,000, preferably 500-20,000. (See HF Mark, Encyclopedia of Polymer Science & Engineering, Vol. 10 , 1-18, J. Wiley 1988).
• the present invention brought about the surprising Result that one observes the invention technical rule excellent shear stability, good Wear protection and long synchronous system service life can combine the lubricating oil additives.
• the oligomer according to the invention caused in Example 1 even at the very high concentrations of 36.1% by weight no interference.
• the desired, very shear-stable multigrade gear oils can be realized to get out of the above For a long time.
• the viscosity n (100 degrees C) is determined in accordance with DIN 51 562 or ASTM D 445 in an Ubbelohde capillary viscometer.
• the molecular weights are determined by gel permeation chromatography against PMMA as the standard.
• the polymerization is also analogous to Example 1 140 degrees C, but with about 1.5 times the amount of tert-butyl perbenzoate carried out.
• the polymerization is carried out analogously to Example 2 at 100 degrees C. and using tert-butyl peroctoate as an initiator carried out.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Publications (3)

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• 1994
  • 1994-02-14 DE DE4404620A patent/DE4404620A1/de not_active Withdrawn
• 1995
  • 1995-02-07 EP EP95101609A patent/EP0667390B1/de not_active Expired - Lifetime
  • 1995-02-07 DE DE59508335T patent/DE59508335D1/de not_active Expired - Lifetime
  • 1995-02-07 AT AT95101609T patent/ATE193050T1/de not_active IP Right Cessation

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