EP0931101A1 - Nouveau polymere en dispersion polymerique comme additif d'indice de viscosite - Google Patents

Nouveau polymere en dispersion polymerique comme additif d'indice de viscosite

Info

Publication number
EP0931101A1
EP0931101A1 EP97942024A EP97942024A EP0931101A1 EP 0931101 A1 EP0931101 A1 EP 0931101A1 EP 97942024 A EP97942024 A EP 97942024A EP 97942024 A EP97942024 A EP 97942024A EP 0931101 A1 EP0931101 A1 EP 0931101A1
Authority
EP
European Patent Office
Prior art keywords
ocp
polymer
meth
pama
molecular weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97942024A
Other languages
German (de)
English (en)
Inventor
Stephan Fengler
Horst Pennewiss
Stephan Massoth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Oil Additives GmbH
Original Assignee
RohMax Additives GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by RohMax Additives GmbH filed Critical RohMax Additives GmbH
Publication of EP0931101A1 publication Critical patent/EP0931101A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/02—Polyethene
    • 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
    • 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
    • C10M2205/022—Ethene
    • 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

Definitions

  • the invention describes a solvent-free polymer dispersion for use as a lubricating oil additive and for improving the viscosity index in lubricating oils.
  • the technology uses large-scale lubricating oil additives based on oil-soluble polymers that improve the viscosity-temperature behavior of multigrade oils (VI improvers).
  • the polymers should lower the pour point of the mineral oil as far as possible and have a dispersing and detergent effect on the sludge and dirt that accumulates in the engine.
  • Two classes of polymers are used primarily for the above-mentioned tasks: lubricating oil additives based on polyalkyl methacrylates (PAMA) and olefin polypropylene (OCP), especially ethylene-propylene copolymers.
  • PAMA polyalkyl methacrylates
  • OCP olefin polypropylene
  • Olefin copolymers have an excellent thickening effect, but they have no pour point depressant action, so pour point improvers must be added to them.
  • pour point improvers must be added to them.
  • association-prone association polyolefins difficulties arise when adding pour point improvers. The difficulty lies in insufficiently lowering the pour point.
  • Polymethacrylates are characterized by a good effect with regard to the viscosity temperature behavior of the oils thus improved and, when added in a sufficiently high concentration, also by an excellent wear protection effect. Also to be emphasized is their pour point depressing effect.
  • DE-OS 3822 134 describes a polymer composition which is suitable as a lubricating oil additive for improving the viscosity index and has the following composition:
  • olefin copolymer with a molecular weight of approximately 30,000 to 200,000 daltons
  • a copolymer of olefins and acrylates and methacrylates c) a polyacrylate or polymethacrylate with a molecular weight of 20,000 to 500,000 daltons and d) a surfactant
  • the surface-active agent d) is an alkylene oxide adduct, which may contain nitrogen.
  • the total polymer content of the preparation is 30-60% by weight, the rest of the preparation consists of mineral oil, for example neutral oil.
  • the surfactant is also added dissolved in mineral oil.
  • the olefin copolymers according to the invention are known. These are primarily those which are composed of ethylene, propylene, butylene and / or isobutylene.
  • Such olefin copolymers are described, for example, in German Offenlegungsschriften DE 16 44 941, DE 17 69 834, DE 19 39 037, DE 19 63 039 and DE 20 59 981.
  • Ethylene-propylene copolymers are preferred, and terpolymers with the addition of the known ter components such as ethylidene norbornene are also possible, but their tendency to crosslink during the aging process must also be taken into account.
  • the distribution of the monomer components in the copolymer can be largely statistical, but sequence polymers with ethylene blocks can also be used with advantages.
  • the ratio of the monomers ethylene to propylene is variable within certain limits, which can be set as the upper limit at approximately 70-75% by weight for ethylene and approximately 30-25% by weight for propylene.
  • polypropylene is already less suitable than ethylene-propylene copolymers.
  • the polyalkyl methacrylates are also known polymers which are composed of methacrylic esters with 6-22 carbon atoms in the alcohol radical, preferably those with 8-18 carbon atoms in the alcohol radical, optionally in minor additional amounts from further monomers which can be copolymerized with the methacrylic acid esters mentioned are.
  • the monomers to be added in minor amounts usually below 20% by weight, it can on the one hand, for. B.
  • monomers with polar groups, in particular suitable polymerizable heterocyclic compounds which are known to contribute to the dispersion, detergent and detergent effects of the base polymers and the anti-wear effect of the base polymers.
  • it can also be polyalkyl methacrylates with 1-5 carbon atoms in the alcohol residue. Methyl methacrylate and butyl methacrylate are particularly preferred.
  • Such monomers or copolymers with methacrylates are such.
  • Graft copolymers of polyolefins with polymerizable nitrogen-containing, in particular heterocyclic, compounds with dispersing action in addition Vl-improving effect are proposed in DE-AS 12 35 491.
  • DE-OS 1 929 811 describes the graft copolymerization of degraded ethylene-propylene copolymers with oxygen-containing comonomers, such as vinyl esters of saturated carboxylic acids, for example vinyl acetate or divinyl esters of carboxylic acids.
  • the exact structure of the graft copolymers obtained is not known; they can be used as additives in a wide variety of lubricants.
  • Vinylpy ⁇ din, vinylpyrrolidine, vinylpyrrolidone and vinylimidazole - and derivatives thereof, in particular the alkylated heterocycles of this type - are particularly worth mentioning as heterocyclic monomers for copolymerization with the methacrylic acid esters mentioned.
  • the nitrogen-containing monomers 2- (4-morpholinyl) ethyl methacrylate is particularly preferred.
  • These heterocyclic monomers can advantageously also be used in combination.
  • the polymer dispersions can be produced in a kneader, an extruder or in a static mixer.
  • the treatment in the device reduces the molecular weight of the OCP under the influence of the shear forces, the temperature and the initiator concentration.
  • Suitable initiators in the graft copolymerization are cumene hydroperoxide, diumyl peroxide, benzoyl peroxide, azodiisobutyric acid dinitrile, 2,2-bis (t-butyl peroxy) butane, diethyl peroxydicarbonate and tert-butyl peroxide.
  • the processing temperature is between 80 ° C and 350 ° C.
  • the residence time in the kneader or extruder is between 1 minute and 10 hours.
  • the temperature and the concentration of free-radical initiators can be adjusted according to the desired molecular weight.
  • the solvent-free polymer-in-polymer dispersion according to the invention can be converted into an easy-to-handle, liquid polymer / polymer emulsion by incorporation into suitable carrier media.
  • Suitable carrier media are described in DE 3207291. At this point, alkoxylated C8-C16 fatty alcohols and alkoxylated alkylphenols should be mentioned.
  • the liquid carrier medium used is one which allows the olefin copolymers to swell to a degree of 5-300% by weight in the temperature range between 40 and 150 ° C. ("degree of swelling").
  • degree of swelling is defined as follows: An OCP film of 1 mm thickness, 2 cm length and 0.5 cm width of known weight is immersed at a different temperature - for example at 90 ° C. - and stored isothermally for 24 hours , removed from the solution with the tweezers, freed of the adhering swelling agent with a filter paper and immediately then balanced.
  • the weight gain in percent - based on the initial weight - is defined as the measure of swelling.
  • the swelling measurement should be carried out at the temperature at which the concentrated OCP emulsion is to be produced. At this temperature, the swelling should be 5-300%. A prerequisite for the applicability of the criterion is that the maximum swelling of the OCP has been reached under the conditions specified above. The degree of swelling is> 200% for good solvents and ⁇ 100% for poor solvents.
  • Carrier media that meet the conditions mentioned include, for. B. to the group of esters and / or to the group of higher alcohols.
  • the molecules of the types of compounds that can be used as carrier medium contain more than 8 carbon atoms per molecule.
  • esters phosphoric acid esters, esters of dicarboxylic acids, esters of monocarboxylic acids with diols or polyalkylene glycols, esters of neopentyl polyols with monocarboxylic acids. (See Ulimann's Encyclopedia of Technical Chemistry, 3rd Edition, Vol. 15, pp. 287-292, Urban & Schwarzenber (1964)).
  • Suitable esters of dicarboxylic acids are the esters of phthalic acid, in particular the phthalic esters with C4 to C ⁇ alcohols, dibutyl phthalate and dioctyl phthalate being particularly mentioned, and then the esters of aliphatic dicarboxylic acids, in particular the esters of straight-chain dicarboxylic acids with branched-chain primary alcohols. Particular emphasis is given to the esters of sebacic, adipic and azainic acid, the 2-ethylhexyl, isooctyl-3,5,5-trimethyl esters and the esters with the Cs, C9 and Cirj oxo alcohols being mentioned in particular should.
  • esters of straight-chain primary alcohols with branched dicarboxylic acids are of particular importance. Examples include the alkyl-substituted adipic acid, for example 2,2,4-trimethyladipic acid.
  • alcohol component come with advantage such.
  • esters of monocarboxylic acids with diols or polyalkylene glycols the di-esters with diethylene glycol, triethylene glycol, tetraethylene glycol to decamethylene glycol, and also with dipropylene glycol as alcohol components should be emphasized.
  • the monocarboxylic acids which are specifically mentioned are propionic acid, (iso) butyric acid and pelargonic acid - for example dipropylene glycol dipelargonate, diethylene glycol dipropionate - and diisobutyyrate as well as the corresponding esters of triethylene glycol and the tetraethylene glycol di-2-ethylhexanoic acid ester.
  • the proportion of the carrier medium in the concentrated polymer emulsion is generally 79 to 25% by weight, preferably less than 70, especially 60 to 40% by weight.
  • This mixture is homogenized at a temperature of 100 ° C. Then 2 g of 2,2-bis (t-butylperoxy) butane and 1 g of t-butylper-2-ethylhexanoate are added and the temperature is raised to 145 ° C. with kneading. After a reaction time of 20 minutes, the reaction mass is removed from the kneader. The product is tack-free up to approx. 50 ° C and can be easily traded in granular form.
  • the viscosity of a 1.7% by weight solution in mineral oil NS 100 corresponds to
  • Example 2 Transfer to a liquid polymer / polymer emulsion
  • the viscosity of a 2.5% by weight solution in mineral oil NS 100 corresponds to
  • Example 3 Preparation of the emulsion in one step
  • the mixture is cooled to 130 ° C. Then 30 g of di-2-ethylhexyl adipate are added and kneaded until homogeneous. Then 70 g of a C12-C14-fatty alcohol-polyethylene glycol ether mixture with an average degree of ethoxylation of 3 mol ethylene oxide are added. This mixture is kneaded at 140 ° C for 2 hours. The mixture is then cooled to room temperature and removed from the kneader. A brownish-white, low-viscosity dispersion is obtained. The polymer content of the emulsion is 50% by weight.
  • the viscosity of a 2.5% by weight solution in mineral oil NS 100 corresponds to

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Lubricants (AREA)

Abstract

La présente invention porte sur une dispersion polymère-en-polymère sans solvant composée de polyalkyl(méth)acrylates (PAMA) et de copolymerisats d'oléfine (OCP) et leur application en tant qu'additif d'indice de viscosité et améliorant de point d'écoulement
EP97942024A 1996-10-11 1997-09-12 Nouveau polymere en dispersion polymerique comme additif d'indice de viscosite Withdrawn EP0931101A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19641954A DE19641954A1 (de) 1996-10-11 1996-10-11 Neue Polymer in Polymer-Dispersion als VI-Verbesserer
DE19641954 1996-10-11
PCT/EP1997/004993 WO1998016566A1 (fr) 1996-10-11 1997-09-12 Nouveau polymere en dispersion polymerique comme additif d'indice de viscosite

Publications (1)

Publication Number Publication Date
EP0931101A1 true EP0931101A1 (fr) 1999-07-28

Family

ID=7808470

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97942024A Withdrawn EP0931101A1 (fr) 1996-10-11 1997-09-12 Nouveau polymere en dispersion polymerique comme additif d'indice de viscosite

Country Status (6)

Country Link
EP (1) EP0931101A1 (fr)
JP (1) JP2001503455A (fr)
AU (1) AU4384897A (fr)
DE (1) DE19641954A1 (fr)
WO (1) WO1998016566A1 (fr)
ZA (1) ZA979103B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10249294A1 (de) 2002-10-22 2004-05-13 Rohmax Additives Gmbh Stabile Polymerdispersionen und Verfahren zur Herstellung
DE10249295A1 (de) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh Polymerdispersionen mit hoher Stabilität und Verfahren zur Herstellung
DE10249292A1 (de) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh Polymerdispersionen mit geringer Viskosität und Verfahren zur Herstellung
JP5676076B2 (ja) * 2008-12-16 2015-02-25 Ｊｘ日鉱日石エネルギー株式会社 潤滑油添加剤組成物及びその製造方法、潤滑油組成物及びその製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862265A (en) * 1971-04-09 1975-01-21 Exxon Research Engineering Co Polymers with improved properties and process therefor
US4026809A (en) * 1974-12-19 1977-05-31 Texaco Inc. Lubricating compositions containing methacrylate ester graft copolymers as useful viscosity index improvers
DE2905954C2 (de) * 1979-02-16 1982-10-28 Röhm GmbH, 6100 Darmstadt Konzentrierte Polymerisatemulsionen als Viskositätsindexverbesserer für Mineralöle
ZA81322B (en) * 1980-01-23 1982-03-31 Rohm & Haas The preparation of graft copolymers, poly (vinyl chloride) compositions containing them and reactors useful in preparing them
CA1264880A (fr) * 1984-07-06 1990-01-23 John Brooke Gardiner Additif d'accroissement de l'indice de viscosite et de dispersion pour huiles lubrifiantes
US4611031A (en) * 1985-01-28 1986-09-09 Rohm And Haas Company Process for the preparation of a compatibilizer for concentrated polymer blends and compatibilizer product
US5128410A (en) * 1988-03-29 1992-07-07 Rohm And Haas Company Graft copolymers and blends thereof with polyolefins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9816566A1 *

Also Published As

Publication number Publication date
ZA979103B (en) 1998-04-23
DE19641954A1 (de) 1998-04-16
WO1998016566A1 (fr) 1998-04-23
AU4384897A (en) 1998-05-11
JP2001503455A (ja) 2001-03-13

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