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
  • C10M145/12—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
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
• • 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
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
  • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M107/28—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
• • 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
  • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
• • 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
  • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
  • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
• • 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
  • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
• • 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
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
• • 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
• • 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
  • C10M2209/084—Acrylate; Methacrylate
  • C10M2209/0845—Acrylate; Methacrylate used as base material
• • 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
  • C10M2209/0863—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 used as base material

Definitions

• the invention relates to synthetic oils which consist wholly or partly of oligomers of or cooligomers of (meth) acrylic acid esters and ⁇ -olefins.
• synthetic oils synthetic oils
• the common synthetic oils belong to different classes of substances, in addition to polyethers, esters (of mono- and polybasic carboxylic acids with mono- and polybasic alcohols), phosphoric acid and phosphonic acid esters, silicones, silicate esters, polyhalocarbons and fluorinated esters, these are polyolefins and alkyl aromatics.
• Polymers obtained from a-olefins of different origins and with different polymerization processes were of particular interest. This is how polymers of a-olefins with 8-12 C atoms come, e.g. by means of Ziegler catalysts or catalysts for ionic polymerization, importance due to their good VI and pour point values. Mixtures of such a-olefin oligomers with ester oils are said to have a relatively good compatibility with rubber materials. Another advantage described is the better miscibility of the olefin oligomer / ester mixtures with polar additives compared to the pure components.
• cooligomers or copolymers of ⁇ -olefins with (meth) acrylic acid esters as mineral oil additives have attracted the interest of technology.
• the included a-olefin greatly improves the thermal stability of the additives.
• US Pat. No. 4,419,106 describes oil preparations which contain a hydrocarbon oil and a portion of a pour point depressant consisting of a copolymer of approx. 10-90% by weight alkyl acrylate units containing 8-20 alkyl C atoms and 90- Have 10% by weight of a-monoolefin units with 12-40 carbon atoms per 100% by weight of copolymer with a molecular weight Mw of 1,000-100,000.
• the narrow molecular weight range achieved and the high uniformity of the products are emphasized.
• US Pat. No. 4,009,195 describes an oligomerization process in which a wide variety of (meth) acrylic acid derivatives, such as, for example, C1-C4-alkyl esters, in proportions of 1-35% by weight in addition to (meth) acrylic acid esters of C8-C34 Alkanols in proportions of 1-45% by weight are added continuously and at the same time to a mixture of radical initiators and 10-90% by weight of a 1-alkene having 4-32 C atoms in such a way that this is essentially immediate occurring molar ratio of acid derivatives to 1-alkene in the reaction mixture is kept relatively constant in the range 0.001 to 0.2, the addition being to take place at a temperature which does not impair the oligomerization.
• DE-A 32 23 694 claims copolymers of ⁇ , ⁇ -unsaturated dicarboxylic acid esters with ⁇ -olefins.
• the ⁇ , ⁇ -unsaturated dicarboxylic acid esters by definition contain straight-chain or branched monoalcohols with 3 to 10 carbon atoms as alcohol components; the a-olefins have 10-16 carbon atoms.
• the copolymers can optionally be crosslinked and their pour point should be between -60 and 0 degrees C.
• Copolymers containing isocyanate groups in the molecular weight range 500-10,000 can be prepared by solution polymerization of C1-C20-alkyl esters of (meth) acrylic acid and olefins with 1-alkenyl isocyanate (cf. DE-A 32 45 298).
• US Pat. No. 4,526,950 describes a production process for copolymers in which, starting from at least one ⁇ -olefin having at least 6 C atoms and at least one unsaturated carboxylic acid or derivatives, copolymerizable with the olefins are, in the presence of a radical initiator, the mixture of the components is heated to at least 135 ° C.
• EP-A 217 602 discloses oil additives based on ethylene copolymers, inter alia with ethylenically unsaturated mono- or dicarboxylic acids or their esters, which have a molecular weight M n of ⁇ 1,000.
• Prior art synthetic oils are usually made from hydrocarbons such as e.g. Oligomers of 1-decene and / or esters, for example dicarboxylic acid esters. (Ullmann's Encyclopedia of Techn. Chemistry, 4th Edition, Vol. 20, 503 - 530, Verlag Chemie 1981).
• esters Due to their polar structure, the esters are known to have serious disadvantages, e.g. Problems with miscibility with mineral oils, non-mineral oil-based base oils and poor seal compatibility. In addition, the ester function can give rise to hydrolysis, with the result that corrosion of metal parts is promoted. Attempts are made to compensate for the disadvantages mentioned by mixing hydrocarbons with esters, but this requires considerable development effort in practice.
• the components A), B) and C) in the cooligomers CM should complement each other 100%.
• the cooligomers according to the invention are in the molecular weight range Mw 1,000 to 100,000, preferably 1,500 to 25,000 (determination by gel permeation chromatography, cf. HF Mark et al. Encyclopedia of Polymer Science & Technology Vol. 10, 1-19, J. Wiley 1987) .
• alkenes-1 having 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.
• component A) of the cooligomers CM stands for 1-decene, dodecene or for tetradecene is particularly preferred. Decen is very particularly preferred, when it is used the best low-temperature behavior (pour point) is registered.
• cooligomers CM in which component B) consists of (meth) acrylic acid esters with 4-24, preferably 8-22, carbon atoms in the alkyl radical or mixtures thereof.
• Cooligomeric CM of the type described are synthetic oil components of the prior art quite comparable in terms of characteristics such as viscosities, VI index, low-temperature behavior, evaporation and oxidation stability and other practical properties.
• oligomers are used as a synthetic oil component, which also contain component C) in sufficient quantity, there is a good dispersing effect, sealing problems being avoided due to the oxygen-containing dispersing group and there being no loss in the shear stability of the mixture, as is the case e.g. occur when using high molecular weight VI improvers.
• Synthetic oils are to be understood in particular as the polyalphaolefins (PAO) preferred by technology and the organic esters (OE) such as dicarboxylic acid and polyol esters (cf. EI Williamson, J. Synth. Lubr. 2 (4) 329-341 (1986) ; 3 (1) 45 - 53 (1987); A. Plagge, Tribologie und Schmtechnikstechnik 34, 148 - 156 (1987); Ullmann, 4th edition, vol. 20, loc.cit. Pp. 514 - 821).
• PAO polyalphaolefins
• OE organic esters
• Crack olefins are primarily used as starting materials for the polyalphaolefins, predominantly with a boiling point between 30 and 300 degrees C.
• the polyalphaolefins generally correspond to the general formula 111 wherein R represents an alkyl radical, in particular having 6-10 carbon atoms, with a molecular weight of usually 300-6000 (Mw).
• Organic esters are, on the one hand, the esters of dicarboxylic acids with 3 to 17 carbon atoms, such as adipic acid, azelaic acid and sebacic acid with primary alcohols - the most important alcohol component in this case are polyalkylene glycols - on the other hand, the monocarboxylic acid esters, especially the esters of C6-C12 carboxylic acids with in particular branched alcohols, especially those with the neopentyl skeleton such as neopentyl alcohol, trimethylolpropane and pentaerythritol.
• the ester oils have a high adsorption capacity on metal surfaces and therefore good lubricity, but at the price of relative sensitivity to (hydrolytic) degradation, so that corrosive degradation products can occur.
• the viscosities range, for example, from around 5.9 [mm 2 / s at 38 degrees C] for the neopentyl glycol ester of n-C7 acid to 16.2 for the corresponding ester of n-C12 acid, or from the value 12 , 1 for the trimethylolpropane ester of n-C6 acid up to a value of 36.4 for the corresponding ester of n-C12 acid.
• the cooligomers of the claimed type can be prepared under certain conditions by radical-induced polymerization, for example by thermal polymerization and with the addition of a suitable initiator or a redox system.
• the polymerization can be carried out in the absence of a solvent or in the presence of suitable solvents.
• all conventional solvents identified as polymerization media can be used, as well as mineral oils, HC oils, PAO, esters or oligomers that have already been produced.
• the 1-alkene according to component A) can be specified in a suitable reaction vessel and brought to a suitable reaction temperature. In general, a temperature range of 80 to 200 degrees C, in particular 160 ⁇ 20 degrees C, can be considered as a suitable range.
• component B) or B) + c) is added in the proportions intended for this purpose in the same temperature range, preferably in the feed over a certain period, for example 0.25-10 hours, for example within 5 1/2 hours. It is expedient to allow the batch to polymerize for some time, usually a few hours - as a reference, about 6 hours. It has proven to be advantageous to add the initiator throughout the reaction, for example in portions at about thirty-minute intervals, or else continuously in the manner of a feed process.
• Known radical initiators can be used as initiators (cf.Kirk-Othmer, 3rd Ed., Vol. 13, pg. 355 - 373, Wiley Interscience 1981; Rauch-Puntigam loc.cit.).
• the total amount of initiator used is generally in the range 0.1-10% by weight, preferably in the range 0.1-5% by weight, based on the total of the monomers.
• Initiators are expediently chosen whose decay characteristics are the polymerization mo dalities are adjusted.
• a guideline is a half-life of the initiator (in benzene) at the reaction temperature of approximately 0.25 hours.
• These include, for example, peroxidic initiators, such as, for example, tert-butyl peroxide.
• the addition of 0.001-0.005 mol of initiator per portion should be given when adding in portions.
• the monomers are largely converted, for example by 98%, so that in many cases there is no need to separate off the monomers or even further work up. If the requirements for the flash point are high, for example, the residual monomer must be removed.
• the products generally are colorless, oily liquids that mix completely with mineral oil, PAO, HC oils and ester oils.
• AMA alkyl methacrylates
• PAO polyalphaolefin
• TMA-OD-Ester ester of trimethylolpropane with adipic acid
• the product is a colorless, oily liquid that is completely miscible with mineral oils, poly-olefins or ester oils.
• reaction temperature but 140 degrees C initiator used: tert-butyl perbenzoate
• reaction temperature 140 degrees C initiator: tert-butyl perbenzoate 4.8% by weight.
• reaction temperature 126 degrees C initiator: tert-butyl personoate 4.8% by weight.
• Example 4 Carried out as in Example 4, but in addition to 1 mol of 1-decene in the initial charge, 280 g of synthetic oil prepared in accordance with Example 4 were used as the solvent.
• methacrylate component is butyl methacrylate, feed time 3.5 hours.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Lubricants (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=6412070

Family Applications (1)

Country Status (5)

Cited By (10)

Families Citing this family (2)

Citations (6)

• 1990
  • 1990-08-11 DE DE4025494A patent/DE4025494A1/de not_active Withdrawn
• 1991
  • 1991-08-05 DK DK91113123.3T patent/DK0471266T3/da active
  • 1991-08-05 AT AT91113123T patent/ATE115995T1/de not_active IP Right Cessation
  • 1991-08-05 EP EP91113123A patent/EP0471266B1/fr not_active Expired - Lifetime
  • 1991-08-05 DE DE59103970T patent/DE59103970D1/de not_active Expired - Lifetime
  • 1991-08-05 ES ES91113123T patent/ES2068441T3/es not_active Expired - Lifetime

Patent Citations (6)

Also Published As

Similar Documents

Legal Events