EP0744457B1 - Lubricant additive - Google Patents
Lubricant additive Download PDFInfo
- Publication number
- EP0744457B1 EP0744457B1 EP96107578A EP96107578A EP0744457B1 EP 0744457 B1 EP0744457 B1 EP 0744457B1 EP 96107578 A EP96107578 A EP 96107578A EP 96107578 A EP96107578 A EP 96107578A EP 0744457 B1 EP0744457 B1 EP 0744457B1
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- EP
- European Patent Office
- Prior art keywords
- meth
- alkyl
- pfp
- group
- acrylic acid
- 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.)
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-
- 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
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
-
- 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
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
Definitions
- the invention relates to the use of macromonomers Graft polymers as lubricant additives with viscosity index improver and dispersant Effect.
- comb polymers comb polymers
- polymeric stabilizers for emulsions compare G. Allen, JC Bevington, Comprehensive Polymer Science Vol. 4 , pg. 248-250, Pergamon Press 1989.
- Access to such comb polymers opens up the radical-initiated copolymerization of macromonomers with (chemically different) comonomers.
- 5,254,632 discloses a relatively simple process for the preparation of suitable macromonomers in which (meth) acrylic acid esters are polymerized in the presence of a hydroxyl-containing sulfur regulator and the resulting hydroxyl-terminated polyalkyl (meth) acrylates with methyl methacrylate give the methacryloyl endblocked poly (meth) acrylate macromonomer transesterification.
- the US patent also contains a compilation of relevant literature in which, inter alia, various ways of preparing the macromonomers are described.
- British application GB-A-1,053,529 relates to oil-soluble copolymers and lubricating oil compositions prepared therefrom.
- the copolymers are prepared by polymerizing esters of acrylic acid or methacrylic acid with relatively long-chain alcohols (C 12 to C 24 ) to a conversion of about 50-90%, then adding methyl and / or ethyl acrylate in a second step and then terminating is polymerized.
- EP-A-0 382 493 describes oil-soluble, amine-containing Copolymers consisting of a main chain and a variety of polymers Side chains with basic amino groups exist.
- the polymers can be prepared by either the amine-containing side chains on a Grafted polymer chain, or by first an amine-containing Macromonomer is prepared, which then with other monomers is copolymerized.
- Comb polymers offer a variety of applications due to the structures of the use as Emulsifiers could claim special interest.
- the structural features did not necessarily seem one particular suitability of such comb polymers as Viscosity Index Improver (VI improver) in Promise lubricating oils.
- VI improver Viscosity Index Improver
- VI improvers in particular dispersing VI improvers as lubricant additives.
- the invention accordingly relates to the use of graft polymers PFP composed of polyalkyl methacrylate macromonomers (A) copolymerized with alkyl (meth) acrylates having C 6 -C 30 -alkyl radicals (AMA) with non-functionalized comonomers (B) selected from the group consisting from alkyl (meth) acrylates with C 1 -C 5 -alkyl radicals, styrene and alkylstyrenes with C 1 -C 4 -alkyl radicals and the vinyl esters and functionalized comonomers (C) selected from the group of (meth) acrylic esters, the (meth) acrylamides , the vinyl heterocycle, in a carrier medium TM as lubricant additives according to claim 1.
- A polyalkyl methacrylate macromonomers
- AMA alkyl (meth) acrylates having C 6 -C 30 -alkyl radicals
- B selected from the group consist
- the biradical radical X is an at least two- and up to 30-membered hydrocarbon chain, preferably with an -S-bridge directly following the polymeric part of I, it being possible for up to 9 carbon atoms to be replaced by ether oxygen.
- the chain can still be replaced by functional radicals of the formula wherein R 9 is hydrogen or an alkyl radical having 1-8 carbon atoms, or a phenyl radical, to be interrupted.
- R 11 is derived from industrial phenols or phenol mixtures are to be considered as particularly favorable.
- the phenol itself mention may be made of tert-butylphenol, octylphenol, nonylphenol, dinonylphenol.
- the functionalized comonomers (C) may belong to the group of formula VIII wherein R 10 is a 5- or 6-membered heterocycle containing at least one nitrogen atom.
- the comonomers of the formula VIII are preferably selected from the group consisting of vinylpyrrolidones, such as 1-vinyl-2-pyrrolidone, vinylimidazole, N-vinylcarbazole, N-vinylsuccinimide, N-vinyloxazolidone, N-vinylphthalimide, vinylpyridines, such as 2-vinylpyridine.
- vinylpyrrolidones such as 1-vinyl-2-pyrrolidone, vinylimidazole, N-vinylcarbazole, N-vinylsuccinimide, N-vinyloxazolidone, N-vinylphthalimide
- vinylpyridines such as 2-vinylpyridine.
- the macromonomer II-A can according to the following Weight relations be constructed: proportion AMA 0 - 90 % By weight, proportion of comonomer (B ') 0-40% by weight, proportion (C') 0 to 100% by weight.
- the compounds of the formula X are obtained by polymerizing the monomers or monomer mixtures of the (meth) acrylic esters in the presence of an OH-functional regulator, preferably a sulfur regulator, for example in the presence of 2-mercaptoethanol (cf. -A 5,254,632).
- OH-functional regulator preferably a sulfur regulator
- 2-mercaptoethanol cf. -A 5,254,632
- X assumes the structure - (CH 2 ) 2 S-.
- other prior art methods which are suitable for producing a PAMA macromonomer having the same monomer composition with relatively high functionality of terminal polymerizable (activated) double bond can also be successfully used (see EP 261 942).
- Suitable carrier medium TM for the graft polymers PFP are preferably inert, predominantly lipophilic solvents of the type customary in additive technology, in particular mineral oils, for example of the SN100 type such as Shell SM 920 or gas oils such as Shell G07.
- the preparation of the macromonomers can in close analogy to US-A 5,254,632 or based on DE-A 23 18 809; W. Radke, AHE Müller, Polym. Prepr. Chem. Soc., Polym. Chem., 32 (1) 1991 and H. Rauch-Puntigam, Th. Völker, acrylic and methacrylic compounds, Springer-Verlag 1967.
- a shielding gas such as For example, nitrogen, for example, to 95 degrees C.
- the initiator for example one usual per compound such as a Perester - called tert.Butyl-2-ethylhexanoate - to and then metered in the AMA monomer preferably in admixture with further initiator, as a basis, about 0.4% by weight Initiator referred to the monomers, while about 3.5 hours too.
- a Perester - called tert.Butyl-2-ethylhexanoate -
- Initiator referred to the monomers
- a suitable reaction vessel for example a 6 l three-necked flask with heating, stirring device, Internal thermometer, air inlet and packed column with regulator-controlled vapor conductor is a mixture of the hydroxyl-containing precursor with methyl (meth) acrylate as an indication, a weight ratio of about 4.3: 3 called - preferably together with at least one known polymerization inhibitor, for example Hydroquinone monomethyl ether and a stabilizer, for example of the HALS type, called e.g. 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide in the usual quantities submitted and expediently under air passage to Heated reflux.
- MMA Assumed transesterification component.
- the transesterification catalyst preferably a lithium compound such as lithium methoxide added as a supporter is about 0.1% based on the Methacrylic acid methyl ester added and continue at reflux held until the boiling point has dropped, about 65 - 68 degrees C. Subsequently, further methanol-rich Distillate withdrawn until by increasing the Boiling temperature - be called about 100 degrees C - a extensive sales is displayed. After distilling off from further distillate (at 100 degrees C) is the approach cooled to room temperature and filtered. The excess methyl ester is advantageously removed on a vacuum rotary evaporator. The macromonomer is obtained A dissolved in the carrier medium TM.
- a mixture is prepared with carrier medium TM added.
- carrier medium TM a smaller part, about 6.5 wt .-% in about 10 times the amount of carrier medium in an apparatus as for the preparation of the hydroxyl group-containing precursor used under an inert gas such as nitrogen on elevated Temperature, as a stop is 82 degrees C, heated.
- a macromonomer A preferably of low molecular weight, together with at least one dispersing monomer C, preferably together with a regulator, in particular a sulfur regulator, may be mentioned as an approximate 0.1% by weight, based on the macromonomers / monomers , submitted and heated under a protective gas such as nitrogen, for example, to 100 degrees C and initiator, for example of the type mentioned and in amounts of about 0.8 wt .-% added.
- a protective gas such as nitrogen
- initiator for example of the type mentioned and in amounts of about 0.8 wt .-% added.
- further initiator is advantageously added in portions of about 1/5 of that already added, and it still lasts for a longer period of time, for about 12 hours at elevated temperature, for example at 100 ° C. Further advantageous variants of the production process can be taken from the examples.
- the graft polymers PFP are distinguished by an outstanding action as a viscosity index improver.
- the improved viscosity-temperature characteristics can be demonstrated by viscosity measurements on model formulations.
- Of particular importance is also the invention to be recorded, excellent dispersing effect.
- the particularly favorable dispersing efficiency is evidenced for example by results of laboratory tests.
- the following examples serve to illustrate the invention.
- the determination of the actual viscosity is carried out according to ASTM D 445.
- the molecular weight is determined by size exclusion chromatography (SEC) using standard PMMA (compare HF Mark et al., Encyclopedia of Polymer Science & Engineering, Vol. 10 , pg., 1-19, J. Wiley, 1987).
- SEC size exclusion chromatography
- PMMA standard PMMA
- Shear Stability Index PSSI Shear Stability Index
- Example A-1a The same apparatus as in Example A-1a) is used.
- the 6 l flask is charged with: 1.396 g of 100 N oil, 155.1 g of methacrylic acid ester of a mixture of C 11 -C 16 -alkanols (product DOBANOL 25L) and 3.10 g of 2-mercaptoethanol and under nitrogen to 110 ° C heated.
- Example A-1a The same apparatus as for Example A-1a).
- the 6 l flask is charged with: 1.396 g of 100 N oil, 155.1 g of methacrylic acid ester of a mixture of C 11 -C 16 -alkanols (product DOBANOL 25L) and 1.55 g of 2-mercaptoethanol and under nitrogen to 110 ° C heated.
- a mixture of 2 448.9 g of the above methacrylic ester, 25.5 g of 2-mercaptopanol and 24.5 g of tert-butyl per 2-ethylhexanoate continuously pumped.
- Example A-1a An apparatus according to Example A-1a is used.
- the monomer mixture is prepared from 227.7 g of macromonomer from Example A-1, 106.3 g of methacrylic acid ester of a mixture of C 11 -C 16 -alkanols (product DOBANOL 25 L) and 45.5 g of methyl methacrylate, 24.5 g of this monomer mixture are charged with 220.5 g of 100 N oil in the apparatus and heated to 82 degrees C under nitrogen.
- Example A-1a The apparatus according to Example A-1a is used. 122.9 g of the macromonomer from Example A-2, 20.0 g of 2- (N-morpholinyl) -ethyl methacrylate and 0.15 g of dodecylmercaptan are placed in the three-necked flask and heated to 100 ° C. under nitrogen and then 1.0 g of tert Butylper-2-ethylhexanoate added. After 3 or 7 hours after the first initiator addition, in each case an additional 0.2 g of tert-butyl per-2-ethylhexanoate is added and the batch is kept at 100 ° C. for a further 12 hours. Yield:: 143 g of oil solution of the comb polymer PFP-2.
- Example A-1 Apparatus as in Example A-1. 122.9 g of the macromonomer from Example A-3, 20 g of 2- (N-morpholinyl) -ethyl methacrylate and 0.15 g of dodecylmercaptan are placed in the three-necked flask and heated to 100 ° C. under nitrogen and then 1.0 g of tertiary Butylper-2-ethylhexanoate added. After 3 or 7 hours after the first initiator addition, in each case a further 0.2 g of initiator is added and the mixture is kept at 100 ° C. for a further 12 hours. Yield: 143 g of oil solution of the comb polymer PFP-3.
- Example A-1 Apparatus as in Example A-1.
- Example A-1 Apparatus as in Example A-1.
- Example A-1a An apparatus according to Example A-1a is used.
- the monomer mixture is prepared from 299.5 g of macromonomer from Example A-1, 65 g of methacrylic acid ester of a mixture of C 11 to C 16 -alkanols (product Dobanol 25 L), 65.0 g of methyl methacrylate and 70.5 g of 100 N oil , 50 g of this monomer mixture are placed in the apparatus and heated to 90 degrees C under nitrogen. After addition of 0.06 g of tert-butyl per-2-ethylhexanoate to the template, 450 g of the monomer mixture are continuously pumped in over 3.5 hours together with 0.59 g of tert-butyl 2-ethylhexanoate.
- Example A-1a An apparatus according to Example A-1a is used.
- the monomer mixture is prepared from 276.5 g macromonomer from Example A-1, 120.0 g n-butyl methacrylate and 103.5 g 100 N oil.
- 75 g of this monomer mixture are placed in the apparatus and heated to 90 degrees C under nitrogen.
- 425 g of the monomer mixture are continuously pumped in over 3.5 hours together with 0.51 g of tert-butyl per-2-ethylhexanoate.
- Example A-1a An apparatus according to Example A-1a is used.
- the monomer mixture is prepared from 207.4 g macromonomer from Example A-1, 165.0 g n-butyl methacrylate and 127.6 g 100 N oil. 75 g of this monomer mixture are introduced into the apparatus and heated to 85 ° C. under nitrogen. After addition of 0.09 g of tert-butyl per-2-ethylhexanoate for submission, 425 g of the monomer mixture are continuously pumped in over 3.5 hours together with 0.51 g of tert-butyl per-2-ethylhexanoate. 1.5 hours after the end of the feed, 250 g of 100 N oil are added for dilution.
- Graft polymers For testing the emulsifier effect of Graft polymers may be the following toluene-water emulsified test for testing the dispersing effect of Soot-spot test can be applied.
- the quantification of the emulsifying effect in% values takes place according to the scheme shown in Fig. 1b. This is the proportion of the observation period 5 minutes to 24 Hours present emulsion by the ratio of Area A is characterized by the total area A + B and in% values specified.
- the additive to be tested is dissolved in 150 N oil (Enerpar 11) mixed two stock solutions: stock solution I with 0.375% polymer content and stock solution II with 0.75% Polymer content. From each stock solution become 2 Soot dispersion solutions prepared (double determination). For this purpose, in each case in a 150 ml beaker 1.5 g of carbon black (Flame black, Degussa special black 4) and 50 g stock solution weighed and then with an Ultra-Turrax Intensive stirrer stirred for 30 minutes at 9,000 u / minute. Thereafter, 20 ⁇ l of each dispersion solution Filter paper (paper Durieux 122) spotted. After 48 Hours of even storage at 30 degrees C will be the Punctuated flecks evaluated. For this, the diameter of the Soot stain and the diameter of the surrounding it Oil spill measured and their ratio in% stated:
- the total score of the spot test is the sum of the four percentage ratings. Products with poor soot dispersion give overall ratings of about 70% and lower, products with good carbon black dispersion give overall ratings of ⁇ 130%.
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Die Erfindung betrifft die Verwendung von aus Makromonomeren gewonnenen Pfropfpolymerisaten als Schmierstoffadditive mit viskositätsindexverbessernder und dispergierender Wirkung.The invention relates to the use of macromonomers Graft polymers as lubricant additives with viscosity index improver and dispersant Effect.
Seit einiger Zeit stehen der Technik sogenannte
Kammpolymere (Comb polymers) zur Verfügung, die beispielsweise
als polymere Stabilisatoren für Emulsionen Anwendung
gefunden haben (vgl. G. Allen, J.C. Bevington,
Comprehensive Polymer Science Vol. 4, pg. 248 - 250,
Pergamon Press 1989).
Einen Zugang zu solchen Kammpolymeren eröffnet die
radikalisch initiierte Copolymerisation von Makromonomeren
mit (chemisch verschiedenen) Comonomeren. Die US-A
5,254,632 gibt ein relativ einfaches Verfahren zur
Herstellung geeigneter Makromonomeren an, bei dem man
(Meth)acrylsäureester in Gegegenwart eines hydroxygruppenhaltigen
Schwefelreglers polymerisiert und die so
erhaltenen hydroxylgruppenterminierten Polyalkyl(meth)-acrylate
mit Methylmethacrylat zum Poly(meth)acrylatmakromonomeren
mit Methacryloylendgruppe umestert. In dem US-Patent
findet sich auch eine Zusammenstellung
einschlägiger Literatur in der u.a. verschiedene Wege zur
Herstellung der Makromonomeren beschrieben werden. For some time, the technology so-called comb polymers (comb polymers) have been available, which have found use, for example, as polymeric stabilizers for emulsions (compare G. Allen, JC Bevington, Comprehensive Polymer Science Vol. 4 , pg. 248-250, Pergamon Press 1989).
Access to such comb polymers opens up the radical-initiated copolymerization of macromonomers with (chemically different) comonomers. US Pat. No. 5,254,632 discloses a relatively simple process for the preparation of suitable macromonomers in which (meth) acrylic acid esters are polymerized in the presence of a hydroxyl-containing sulfur regulator and the resulting hydroxyl-terminated polyalkyl (meth) acrylates with methyl methacrylate give the methacryloyl endblocked poly (meth) acrylate macromonomer transesterification. The US patent also contains a compilation of relevant literature in which, inter alia, various ways of preparing the macromonomers are described.
Die britische Anmeldung GB-A-1,053,529 betrifft öllösliche Copolymere und daraus hergestellte Schmierölzusammensetzungen. Die Copolymere werden hergestellt, indem Ester der Acrylsäure oder Methacrylsäure mit längerkettigen Alkoholen (C12 bis C24) bis zu einem Umsatz von etwa 50 - 90 % polymerisiert werden, dann in einem zweiten Schritt Methyl- und/oder Ethylacrylat zugegeben und anschließend zu Ende polymerisiert wird.British application GB-A-1,053,529 relates to oil-soluble copolymers and lubricating oil compositions prepared therefrom. The copolymers are prepared by polymerizing esters of acrylic acid or methacrylic acid with relatively long-chain alcohols (C 12 to C 24 ) to a conversion of about 50-90%, then adding methyl and / or ethyl acrylate in a second step and then terminating is polymerized.
Die europäische Anmeldung EP-A-0 382 493 beschreibt öllösliche, aminhaltige Copolymere, die aus einer Hauptkette und einer Vielzahl von polymeren Seitenketten mit basischen Aminogruppen bestehen. Die Polymere können hergestellt werden, indem entweder die aminhaltigen Seitenketten auf eine Polymerkette aufgepropft werden, oder indem zuerst ein amingruppen-haltiges Makromonomer hergestellt wird, welches dann mit weiteren Monomeren copolymerisiert wird. European application EP-A-0 382 493 describes oil-soluble, amine-containing Copolymers consisting of a main chain and a variety of polymers Side chains with basic amino groups exist. The polymers can be prepared by either the amine-containing side chains on a Grafted polymer chain, or by first an amine-containing Macromonomer is prepared, which then with other monomers is copolymerized.
Die aus den geschilderten Entwicklungen ableitbaren Kammpolymeren bieten sich für mannigfaltige Anwendungsbereiche an, wobei aufgrund der Strukturen der Einsatz als Emulgatoren besonderes Interesse beanspruchen konnte. Die strukturellen Merkmale schienen nicht unbedingt eine besondere Eignung derartiger Kammpolymerer als Viskositäts-Index-Verbesserer (VI-Verbesserer) in Schmierölen zu versprechen.The derivable from the described developments Comb polymers offer a variety of applications due to the structures of the use as Emulsifiers could claim special interest. The structural features did not necessarily seem one particular suitability of such comb polymers as Viscosity Index Improver (VI improver) in Promise lubricating oils.
Andererseits besteht durchaus ein Bedürfnis nach wirksamen VI-Verbesserern, insbesondere auch dispergierwirksamen VI-Verbesserern als Schmierstoffadditive.On the other hand, there is a need for effective VI improvers, in particular dispersing VI improvers as lubricant additives.
Es wurde nun gefunden, daß die erfindungsgemäßen Schmierstoffadditive auf der Basis von bestimmten Kammpolymeren die Anforderungen der Schmierstofftechnik in besonderem Maße erfüllen.It has now been found that the inventive Lubricant additives based on certain Comb polymers the requirements of the lubricant technology in fulfill special requirements.
Die Erfindung betrifft demnach die Verwendung von
Pfropfpolymeren
PFP aufgebaut aus Polyalkylmethacrylat-Makromonomeren (A),
copolymerisiert mit Alkyl(meth)acrylsäureestern mit C6-C30-Alkylresten
(AMA), mit nicht-funktionalisierten
Comonomeren (B) ausgewählt aus der Gruppe bestehend aus
Alkyl(meth)acrylsäureestern mit C1-C5-Alkylresten, Styrol
und Alkylstyrolen mit C1-C4-Alkylresten und der Vinylester
sowie funktionalisierten Comonomeren (C) ausgewählt aus
der Gruppe der (Meth)acrylsäureester, der
(Meth)acrylamide, der Vinyl-Heterocyclen, in einem
Trägermedium TM als Schmierstoffadditive gemäß dem Anspruch 1.The invention accordingly relates to the use of graft polymers PFP composed of polyalkyl methacrylate macromonomers (A) copolymerized with alkyl (meth) acrylates having C 6 -C 30 -alkyl radicals (AMA) with non-functionalized comonomers (B) selected from the group consisting from alkyl (meth) acrylates with C 1 -C 5 -alkyl radicals, styrene and alkylstyrenes with C 1 -C 4 -alkyl radicals and the vinyl esters and functionalized comonomers (C) selected from the group of (meth) acrylic esters, the (meth) acrylamides , the vinyl heterocycle, in a carrier medium TM as lubricant additives according to
In der Regel stehen die Komponenten, aus denen die Pfropfpolymere PFP aufgebaut sind in folgenden Gewichtsrelationen: (Summe der Anteile im allgem. = 100 Gew.-%) In general, the components that make up the Graft polymers PFP are constructed in the following Weight relations: (sum of the shares in general = 100% by weight)
Makromonomere (A) = 10 - 90 Gew.-%, Alkyl(meth)acrylsäureester mit C6-C30-Alkylresten, (AMA) = 0 - 90 Gew.-% Nichtfunktionalisierte Comonomere, (B) = 0 - 60 Gew.-% und funktionalisierte Comonomere (C) = 0 - 40 Gew.-%.Macromonomers (A) = 10 - 90 wt .-%, alkyl (meth) acrylic acid esters with C 6 -C 30 -alkyl radicals, (AMA) = 0 - 90 wt .-% of non-functionalized comonomers, (B) = 0 - 60 wt. % and functionalized comonomers (C) = 0-40% by weight.
In einer bevorzugten Ausführungsart der Erfindung kann die Struktur der anzuwendenden Pfropfpolymere PFP schematisch durch die folgende Formel I wiedergegeben werden, jedoch fallen auch abweichende Ausgestaltungen unter die vorliegende Erfindung.
- X =
- biradikalischer Rest
- R1 =
- -H oder -CH3
- R2 =
- -H oder -CH3
- R3 =
- -H oder -CH3
- n =
- 6 bis 30
- m =
- 6 bis 30
- p =
- mittlerer Polymerisationsgrad des Makromonomeren (A)
- X =
- biradical residue
- R 1 =
- -H or -CH 3
- R 2 =
- -H or -CH 3
- R 3 =
- -H or -CH 3
- n =
- 6 to 30
- m =
- 6 to 30
- p =
- average degree of polymerization of the macromonomer (A)
Bei der Herstellung der Pfropfpolymeren PFP kann vorzugsweise von dem Makromonomeren der Formel II ausgegangen werden:
- X =
- biradikalischer Rest
- R1 =
- -H oder -CH3
- R2 =
- -H oder -CH3
- n =
- 6 bis 30
- p =
- mittlerer Polymerisationsgrad des Makromonomeren
- X =
- biradical residue
- R 1 =
- -H or -CH 3
- R 2 =
- -H or -CH 3
- n =
- 6 to 30
- p =
- average degree of polymerization of the macromonomer
Dabei ist p vorzugsweise so bemessen, daß MW das
gewichtsmittlere Molekulargewicht des Makromonomeren der
Formel II im Bereich 1 000 bis 100 000 liegt.
Vorzugsweise steht der biradikalische Rest X für eine
mindestens zwei- und bis 30-gliedrige KohlenwasserstoffKette,
vorzugsweise mit einer -S-Brücke direkt
anschließend an den polymeren Teil von I, wobei
gegebenenfalls bis 9 Kohlenstoffglieder durch
Ethersauerstoff ersetzt sein können. Ferner kann im Rest X
die Kette noch durch funktionelle Reste der Formel
worin R9 für
Wasserstoff oder einen Alkylrest mit 1 - 8 Kohlenstoffatomen
steht, oder einen Phenylrest, unterbrochen sein. In this case, p is preferably such that M W is the weight-average molecular weight of the macromonomer of the formula II in the range from 1 000 to 100 000.
Preferably, the biradical radical X is an at least two- and up to 30-membered hydrocarbon chain, preferably with an -S-bridge directly following the polymeric part of I, it being possible for up to 9 carbon atoms to be replaced by ether oxygen. Furthermore, in the radical X, the chain can still be replaced by functional radicals of the formula wherein R 9 is hydrogen or an alkyl radical having 1-8 carbon atoms, or a phenyl radical, to be interrupted.
Die Alkyl(meth)acrylate AMA lassen sich im allgemeinen durch die Formel III ausdrücken:
- R'1 =
- H oder CH3
- n =
- 6 bis 30
- R ' 1 =
- H or CH 3
- n =
- 6 to 30
Die Comonomeren (B) entsprechen in der Regel den Formeln IV oder V
- R"1 =
- H oder CH3
- R3 =
- C1-C5-Alkyl, vorzugsweise C1-C4-Alkyl
- R'''1 =
- H oder CH3
- R4 =
- H oder C1-C4-Alkyl
- R5 =
- C1-C11-Alkyl,
- R " 1 =
- H or CH 3
- R 3 =
- C 1 -C 5 -alkyl, preferably C 1 -C 4 -alkyl
- R ''' 1 =
- H or CH 3
- R 4 =
- H or C 1 -C 4 -alkyl
- R 5 =
- C 1 -C 11 -alkyl,
Genannt seien als Vertreter der Comonomeren der Formel VI das Vinylacetat, Vinylpropionat, Vinylisobutyrat, Vinyl-2-ethylhexoat, Vinylester der Kokosfettsäuren, der C10-Oxosäuren (vgl. Kirk-Othmer, 3rd. Ed. Vol. 4, 863 - 871, J. Wiley 1978), als Vertreter der Formel IV insbesondere das Methylmethacrylat (Monomer IV-a).Mention may be made as representatives of the comonomers of the formula VI, the vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl 2-ethylhexoate, vinyl esters of coconut fatty acids, the C 10 -oxo acids (see Kirk-Othmer, 3rd Ed., Vol 4 , 863-871, J. Wiley 1978), as a representative of the formula IV, in particular the methyl methacrylate (monomer IV-a).
Die (mit den vorgenannten Comonomeren nicht identischen)
funktionalisierten, insbesondere dispergierwirksamen
Comonomeren (C) können bevorzugt durch die Formel VII
wiedergegeben werden:
worin RIV 1 für Wasserstoff oder Methyl, R6 für -OR9 -NR7R8
steht und worin R9 für einen mit mindestens einem
hydrophilen Rest A ausgewählt aus der Gruppe bestehend aus
dem Hydroxyrest, einem -NR'7R'8 Rest, dem Sulfonsäurerest,
dem Carboxylrest oder Carboxamidrest oder eine, an sich
wasserlöslichen, fünf- bis sechsgliedrigen Heterocyclussubstituierten
Alkylrest mit 2 bis 20 Kohlenstoffatomen,
wobei die Kohlenstoffkette durch Etherbrücken unterbrochen
oder endständig mit einem gegebenenfalls mit C1-C12-Alkylsubstituierten
Phenyl- oder Phenoxyrest besetzt sein kann
und worin R'7 und R'8 für Wasserstoff oder für einen
gegebenenfalls mit einem hydrophilen Rest A substituierten
Alkylrest mit 1 bis 6 Kohlenstoffatomen stehen oder worin
R'7 und R'8 gegebenenfalls unter Einbeziehung weiterer
Stickstoff- oder Sauerstoffatome einen 5- oder 6-gliedrigen
Heterocyclus bilden und worin R'7 und R'8 für
Wasserstoff oder einen Alkylrest mit 1 bis 6
Kohlenstoffatomen steht, wobei -NR'7R'8 gegebenenfalls
quaterniert sein kann oder wenn R7 für Wasserstoff steht
R8 für eine Carboxamidogruppe stehen kann. Vorzugsweise
sind die funktionalisierten Comonomeren (C) ausgewählt aus
der Gruppe bestehend aus gegebenenfalls substituierten
(Meth)acrylamid, Hydroxyalkylestern der (Meth)acrylsäure
wie 2-Hydroxyethyl(meth)acrylat, 2-Hydroxyropyl(meth)-acrylat,
aminsubstituierte Alkylester wie 2-Diethylaminoethyl(meth)acrylat,
2-(1-Imidazolyl)ethyl(meth)acrylat,
2-(4-Morpholinyl)ethyl(meth)acrylat, 2-Trimethylammoniumethyl(meth)acrylat-Salz,
hydroxalkylsubstituierten (Meth)acrylamiden wie N-(2-Hydroxyethyl)(meth)acrylamid,
N-(3-Hydroxy-2,2-dimethylpropyl)
(meth)acrylamid, N-Dimethylaminomethyl(meth)-acrylamid,
N-(meth)acryloidopyrrolidon-2-, N-(Meth)acrylamidomethylpyrrolidon,
N-(1-Piperidinylmethyl)-(meth)acrylamid,
quaternäre Ammoniumverbindungen wie N-Trimethylammoniumpropyl(meth)acrylamid-Salz,
Sulfonsäurederivate wie 2-(Meth)acrylamido-2-methylpropansulfonsäure
oder den N-(Meth)acryloylharnstoff.
Genannt seien insbesondere das 2-(N-Morpholinyl)ethylmethacrylat
(= Monomer VII-a), N-Vinylpyrrolidon (=
Monomer VIII-a).
Von besonderem Interesse sind Monomere der Formel VII
worin R6 für den Rest eines alkoxylierten Alkanols oder
Phenols steht (Comonomere der Formel VII-A).
- R'1 =
- -H oder -CH3
- k =
- 5
bis 100 - i =
- 0
bis 100 - R11 =
- CnH2n+1 verzweigt oder unverzweigt oder gegebenenfalls substituiertes Phenol
- n =
- 1 bis 22
Of particular interest are monomers of the formula VII in which R 6 is the radical of an alkoxylated alkanol or phenol (comonomers of the formula VII-A).
- R ' 1 =
- -H or -CH 3
- k =
- 5 to 100
- i =
- 0 to 100
- R 11 =
- C n H 2n + 1 branched or unbranched or optionally substituted phenol
- n =
- 1 to 22
Als besonders günstig sind Vertreter der Formel VII-A
einzuschätzen, bei denen R11 von technischen Phenolen bzw.
Phenolgemischen stammt. Genannt seien neben dem Phenol
selbst tert.Butylphenol, Octylphenol, Nonylphenol,
Dinonylphenol.
Ferner können die funktionalisierten Comonomeren (C) der
Gruppe der Formel VIII angehören
worin R10 für einen mindestens ein Stickstoffatom
enthaltenden 5- oder 6-gliedrigen Heterocyclus steht.
Vorzugsweise sind die Comonomeren der Formel VIII
ausgewählt aus der Gruppe bestehend aus Vinylpyrrolidone
wie das 1-Vinyl-2-pyrrolidon, Vinylimidazol, N-Vinylcarbazol,
N-Vinylsuccinimid, N-Vinyloxazolidon, N-Vinylphthalimid,
Vinylpyridine wie das 2-Vinylpyridin.Representatives of the formula VII-A in which R 11 is derived from industrial phenols or phenol mixtures are to be considered as particularly favorable. In addition to the phenol itself, mention may be made of tert-butylphenol, octylphenol, nonylphenol, dinonylphenol.
Furthermore, the functionalized comonomers (C) may belong to the group of formula VIII wherein R 10 is a 5- or 6-membered heterocycle containing at least one nitrogen atom. The comonomers of the formula VIII are preferably selected from the group consisting of vinylpyrrolidones, such as 1-vinyl-2-pyrrolidone, vinylimidazole, N-vinylcarbazole, N-vinylsuccinimide, N-vinyloxazolidone, N-vinylphthalimide, vinylpyridines, such as 2-vinylpyridine.
Als Ausgangsprodukte für die Herstellung der Pfropfpolymeren PFP können auch funktionalisierte Poly(meth)acrylat-Makromonomere eingesetzt werden. Vorzugsweise fallen diese unter die Formel II-A
- R1 =
- -H oder -CH3
- R2 =
- -H oder -CH3
- n =
- 6 bis 30
- R 1 =
- -H or -CH 3
- R 2 =
- -H or -CH 3
- n =
- 6 to 30
Gewichtsmittleres Molekulargewicht des Makromonomeren: Mw = 1 000 bis 100 000.Weight-average molecular weight of the macromonomer: M w = 1,000 to 100,000.
Das Makromonomer II-A kann dabei nach den folgenden Gewichtsrelationen aufgebaut sein: Anteil AMA 0 - 90 Gew.-%, Anteil Comonomer (B') 0 - 40 Gew.-%, Anteil (C') 0 bis 100 Gew.-%.The macromonomer II-A can according to the following Weight relations be constructed: proportion AMA 0 - 90 % By weight, proportion of comonomer (B ') 0-40% by weight, proportion (C') 0 to 100% by weight.
Die vorliegende Erfindung kann sich vorteilhaft des Verfahrens zur Herstellung von Makromonomeren der allgemeinen Formel II worin
- R1 und R2
- für Wasserstoff oder Methyl
- X
- für einen biradikalischen Rest und
- n
- für eine ganze
Zahl von 5 bis 30 steht, mit der Maßgabe, daß p so bemessen ist, daß das Molekulargewicht M der MakromonomerenII im Bereich 1 000 bis 100000 g/mol liegt,
- R12
- für einen Alkylrest
mit 1 bis 8 Kohlenstoffatomen steht mit einem hydroxylgruppenterminierten Polyalkylmethacrylat der Formel X
- R 1 and R 2
- for hydrogen or methyl
- X
- for a biradical rest and
- n
- is an integer from 5 to 30, with the proviso that p is such that the molecular weight M of the macromonomers II is in the range 1000 to 100000 g / mol,
- R 12
- represents an alkyl radical having 1 to 8 carbon atoms with a hydroxyl-terminated polyalkyl methacrylate of the formula X.
Nach dem bevorzugten Herstellungsverfahren der
Makromonomeren erhält man die Verbindungen der Formel X
indem man die Monomeren bzw. Monomerengemische der
(Meth)acrylester in Gegenwart eines OH-funktionellen
Reglers, vorzugsweise eines Schwefelreglers,
polymerisiert, beispielsweise in Gegenwart von 2-Mercaptoethanol
(vgl. US-A 5,254,632). Im letzteren Falle
nimmt X die Struktur -(CH2)2S- an. Jedoch können mit gutem
Erfolg auch andere Methoden des Standes der Technik zur
Anwendung kommen, die zur Herstellung eines PAMA-Makromonomeren
mit gleicher Monomerzusammensetzung mit
relativ hoher Funktionalität an endständiger
polymerisierbarer (aktivierter) Doppelbindung geeignet
sind (vgl. EP 261 942). Von besonderer Bedeutung sind
Makromonomere (A) aufgebaut aus (Meth)acrylsäureestern von
handelsüblichen Gemischen von Alkoholen in dem
beanspruchten C6-C30-Bereich, insbesondere im Bereich
mittlerer C-Zahlen von ca. 10 bis ca. 20, besonders auch
im Bereich von ca. 12 - 18, speziell mit Schwerpunkten in
den Bereichen 12,2 - 15. Genannt seien z.B. die
(Methacrylsäureester eines Gemischs von C11-C16-Alkoholen
mit einer durchschnittlichen C-Zahl von 13,2 - 13,8
(Handelsprodukt DOBANOL 25L der Shell AG).
Als Trägermedium TM für die Pfropfpolymeren PFP kommen
vorzugsweise inerte, vorwiegend lipophile Lösemittel der
in der Additivtechnologie üblichen Art infrage,
insbesondere Mineralöle beispielsweise vom Typ der SN100
wie z.B. Shell SM 920 oder auch Gasöle wie z.B. Shell
G07.
Die Herstellung der Makromonomeren kann in enger Analogie
zur US-A 5,254,632 bzw. in Anlehnung an DE-A 23 18 809; W.
Radke, A.H.E. Müller, Polym. Prepr. (Am. Chem. Soc. Div.
Polym. Chem) 32(1) 1991 und H. Rauch-Puntigam, Th. Völker,
Acryl- und Methacrylverbindungen, Springer-Verlag 1967
vorgenommen werden.According to the preferred preparation process of the macromonomers, the compounds of the formula X are obtained by polymerizing the monomers or monomer mixtures of the (meth) acrylic esters in the presence of an OH-functional regulator, preferably a sulfur regulator, for example in the presence of 2-mercaptoethanol (cf. -A 5,254,632). In the latter case, X assumes the structure - (CH 2 ) 2 S-. However, other prior art methods which are suitable for producing a PAMA macromonomer having the same monomer composition with relatively high functionality of terminal polymerizable (activated) double bond can also be successfully used (see EP 261 942). Of particular importance are macromonomers (A) synthesized from (meth) acrylic acid esters of commercially available mixtures of alcohols in the claimed C 6 -C 30 range, in particular in the range of average C numbers of about 10 to about 20, especially in the range from about 12 to 18, especially with emphasis in the areas 12.2 to 15. Mention may be made, for example, of the (methacrylic acid esters of a mixture of C 11 -C 16 -alcohols having an average C number of 13.2 to 13.8 ( Commercial product DOBANOL 25L from Shell AG).
Suitable carrier medium TM for the graft polymers PFP are preferably inert, predominantly lipophilic solvents of the type customary in additive technology, in particular mineral oils, for example of the SN100 type such as Shell SM 920 or gas oils such as Shell G07.
The preparation of the macromonomers can in close analogy to US-A 5,254,632 or based on DE-A 23 18 809; W. Radke, AHE Müller, Polym. Prepr. Chem. Soc., Polym. Chem., 32 (1) 1991 and H. Rauch-Puntigam, Th. Völker, acrylic and methacrylic compounds, Springer-Verlag 1967.
Zweckmäßig gibt man ein Gemisch aus den Alkyl(meth)-acrylaten AMA zusammen mit dem Molekulargewichtsregler, wie beispielsweise Mercaptoethanol - als Anhalt seien ca. 1,0 Gew.-% bezogen auf die Monomeren genannt - in einem geeigneten Reaktionsgefäß wie z.B. einem Dreihalskolben mit Heizung, Rührvorrichtung, Innenthermometer, Gaseinleitungsvorrichtung und Rückflußkühler in beispielsweise der etwa 10-fachen Menge des Trägermediums TM vor und erhitzt unter Einleitung eines Schutzgases wie beispielsweise Stickstoff, beispielsweise auf 95 Grad C. Man gibt nunmehr den Initiator, beispielsweise eine an sich übliche Perverbindung wie beispielsweise einen Perester - genannt sei tert.Butyl-2-ethylhexanoat - zu und dosiert dann das AMA-Monomer vorzugsweise im Gemisch mit weiterem Initiator, als Anhalt seien etwa 0,4 Gew-% Initiator bezogen auf die Monomeren genannt, während etwa 3,5 Stunden zu. Vorteilhafterweise gibt man nach Zulaufende in gewissen Abständen - etwa nach jeweils 2,5 und nach 5 Stunden - ca. die Hälfte des Initiators zu und hält über einen längeren Zeitraum, etwa 12 Stunden, bei ca. 95 Grad C. Anschließend verdünnt man zweckmäßig mit dem Trägermedium TM.It is expedient to add a mixture of the alkyl (meth) acrylates AMA together with the molecular weight regulator, such as mercaptoethanol - as a basis, approx. 1.0 wt .-% based on the monomers called - in one suitable reaction vessel such as e.g. a three-necked flask with heating, stirrer, internal thermometer, Gas introduction device and reflux condenser in for example, about 10 times the amount of the carrier medium TM and heated under introduction of a shielding gas such as For example, nitrogen, for example, to 95 degrees C. One now specifies the initiator, for example one usual per compound such as a Perester - called tert.Butyl-2-ethylhexanoate - to and then metered in the AMA monomer preferably in admixture with further initiator, as a basis, about 0.4% by weight Initiator referred to the monomers, while about 3.5 hours too. Advantageously, one gives way Incoming ends at intervals - about every 2.5 and after 5 hours - about half of the initiator to and Stays for a longer period, about 12 hours about 95 degrees C. Then you dilute appropriately with the carrier medium TM.
In einem geeigneten Reaktionsgefäß, beispielsweise einem 6 l Dreihalskolben mit Heizung, Rührvorrichtung, Innenthermometer, Lufteinleitung und Füllkörperkolonne mit reglergesteuertem Dampfleiter wird ein Gemisch aus der hydroxylgruppenhaltigen Vorstufe mit Methyl(meth)acrylat - als Anhalt sei ein Gewichtsverhältnis von etwa 4,3 : 3 genannt - vorzugsweise zusammen mit mindestens einem an sich bekannten Polymerisationsinhibitor, beispielsweise Hydrochinonmonomethylether und einem Stabilisator, beispielsweise vom HALS-Typ, genannt sei z.B. 4-Hydroxy-2,2,6,6-tetramethylpiperidin-1-oxid in den üblichen Mengen vorgelegt und zweckmäßig unter Luftdurchleitung zum Rückfluß erwärmt. Im folgenden wird MMA als Umesterungskomponente vorausgesetzt. Nachdem ein gewisser Anteil übergegangen ist, wird der Umesterungskatalysator; vorzugsweise eine Lithium-Verbindung wie Lithiummethoxid zugesetzt, als Anhalt sei etwa 0,1 % bezogen auf den Methacrylsäuremethylester zugesetzt und weiter am Rückfluß gehalten, bis die Siedetemperatur abgefallen ist, etwa auf 65 - 68 Grad C. Anschließend wird weiter Methanol-reiches Destillat abgezogen bis durch Anstieg der Siedetemperatur - genannt seien etwa 100 Grad C - ein weitgehender Umsatz angezeigt wird. Nach Abdestillieren von weiterem Destillat (bei 100 Grad C) wird der Ansatz auf Raumtemperatur gekühlt und filtriert. Den überschüssigen Methylester entfernt man vorteilhafterweise am Vakuumrotationsverdampfer. Man erhält das Makromonomere A in dem Trägermedium TM gelöst.In a suitable reaction vessel, for example a 6 l three-necked flask with heating, stirring device, Internal thermometer, air inlet and packed column with regulator-controlled vapor conductor is a mixture of the hydroxyl-containing precursor with methyl (meth) acrylate as an indication, a weight ratio of about 4.3: 3 called - preferably together with at least one known polymerization inhibitor, for example Hydroquinone monomethyl ether and a stabilizer, for example of the HALS type, called e.g. 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide in the usual quantities submitted and expediently under air passage to Heated reflux. The following is MMA as Assumed transesterification component. After a certain Share is transferred, the transesterification catalyst; preferably a lithium compound such as lithium methoxide added as a supporter is about 0.1% based on the Methacrylic acid methyl ester added and continue at reflux held until the boiling point has dropped, about 65 - 68 degrees C. Subsequently, further methanol-rich Distillate withdrawn until by increasing the Boiling temperature - be called about 100 degrees C - a extensive sales is displayed. After distilling off from further distillate (at 100 degrees C) is the approach cooled to room temperature and filtered. The excess methyl ester is advantageously removed on a vacuum rotary evaporator. The macromonomer is obtained A dissolved in the carrier medium TM.
Aus dem vorzugsweise wie vorstehend beschrieben hergestellten Makromonomeren A sowie dem AMA-Monomeren und gegebenenfalls dem Comonomeren B im gewünschten Verhältnis wird eine Mischung hergestellt, mit Trägermedium TM versetzt. Davon wird ein kleinerer Teil, etwa 6,5 Gew.-% in ca. der 10-fachen Menge Trägermedium in einer Apparatur wie zur Herstellung der hydroxylgruppenhaltigen Vorstufe verwendet unter einem Schutzgas wie Stickstoff auf erhöhte Temperatur, als Anhalt seien 82 Grad C genannt, erwärmt. Nach Zugabe von Radikalinitiator zu der Vorlage setzt man innerhalb eines gewissen Zeitraums, beispielsweise 3,5 Stunden, die weitere Monomermischung zusammen mit Initiator zu, zweckmäßig durch kontinuierliches Zupumpen. Nach einem längeren Zeitabschnitt ab Zulaufende, genannt seien ca. 12 Stunden, wird weiterer Initiator zugegeben und noch einige Stunden, beispielsweise 8 Stunden, bei erhöhter Temperatur (ca. 82 Grad C) reagieren lassen. Anschließend wird zweckmäßig durch Zugabe von Trägermedium TM verdünnt (z.B. zu einer ca. 40 %igen Lösung).From the preferably as described above prepared macromonomer A and the AMA monomers and optionally the comonomer B in the desired ratio a mixture is prepared with carrier medium TM added. Of which, a smaller part, about 6.5 wt .-% in about 10 times the amount of carrier medium in an apparatus as for the preparation of the hydroxyl group-containing precursor used under an inert gas such as nitrogen on elevated Temperature, as a stop is 82 degrees C, heated. After adding radical initiator to the template, place within a certain period of time, for example 3.5 Hours, the more monomer mixture along with Initiator to, expediently by continuous pumping. After a longer period of time from the inlet end, called be about 12 hours, more initiator is added and a few more hours, for example 8 hours elevated temperature (about 82 degrees C) react. It is then expedient by adding carrier medium TM (e.g., to about 40% solution).
In der vorstehend beschriebenen Apparatur wird ein
Makromonomer A, vorzugsweise mit niederem Molekulargewicht
zusammen mit mindestens einem dispergierwirksamen
Monomeren C, vorzugsweise zusammen mit einem Regler,
insbesondere einem Schwefelregler, als Anhalt seien etwa
0,1 Gew.-% bezogen auf die Makromonomeren/Monomeren
genannt, vorgelegt und unter einem Schutzgas wie
beispielsweise Stickstoff erwärmt, beispielsweise auf 100
Grad C und Initiator beispielsweise der genannten Art und
in Mengen von ca. 0,8 Gew.-% zugegeben. Man gibt
vorteilhaft im Abstand einiger Stunden, beispielsweise
nach 3 und 7 Stunden noch weiteren Initiator vorteilhaft
in Portionen von etwa 1/5 des bereits zugesetzten hinzu
und hält noch über einen längeren Zeitraum, etwa 12
Stunden bei erhöhter Temperatur, beispielsweise bei
100 Grad C.
Weitere vorteilhafte Varianten der Herstellungsverfahren
lassen sich den Beispielen entnehmen.In the apparatus described above, a macromonomer A, preferably of low molecular weight, together with at least one dispersing monomer C, preferably together with a regulator, in particular a sulfur regulator, may be mentioned as an approximate 0.1% by weight, based on the macromonomers / monomers , submitted and heated under a protective gas such as nitrogen, for example, to 100 degrees C and initiator, for example of the type mentioned and in amounts of about 0.8 wt .-% added. Advantageously, at intervals of a few hours, for example after 3 and 7 hours, further initiator is advantageously added in portions of about 1/5 of that already added, and it still lasts for a longer period of time, for about 12 hours at elevated temperature, for example at 100 ° C.
Further advantageous variants of the production process can be taken from the examples.
Die Pfropfpolymerisate PFP zeichnen sich
durch eine hervorragende Wirkung als Viskositäts-Index-Verbesserer
aus. Die verbesserte Viskositäts-Temperatur-Charakteristik
kann anhand von Viskositätsmessungen an
Modell-Formulierungen demonstriert werden.
Von besonderer Bedeutung ist ferner die erfindungsgemäß zu
verzeichnende, ausgezeichnete Dispergierwirkung. Die
besonders günstige Dispergierwirksamkeit wird z.B. durch
Ergebnisse von Labortests belegt.The graft polymers PFP are distinguished by an outstanding action as a viscosity index improver. The improved viscosity-temperature characteristics can be demonstrated by viscosity measurements on model formulations.
Of particular importance is also the invention to be recorded, excellent dispersing effect. The particularly favorable dispersing efficiency is evidenced for example by results of laboratory tests.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung. Die Bestimmung der aktuellen Viskosität wird nach ASTM D 445 vorgenommen. Das Molgewicht wird durch "Size Exclusion Chromatographie" (SEC) mit Standard PMMA bestimmt (vgl. H.F. Mark et al. Encyclopedia of Polymer Science & Engingeering, Vol. 10, pg. 1 - 19, J. Wiley 1987). Das in den Beispielen verwendete 100 N-Öl stellt ein Shell SM 920 dar.The following examples serve to illustrate the invention. The determination of the actual viscosity is carried out according to ASTM D 445. The molecular weight is determined by size exclusion chromatography (SEC) using standard PMMA (compare HF Mark et al., Encyclopedia of Polymer Science & Engineering, Vol. 10 , pg., 1-19, J. Wiley, 1987). The 100 N oil used in the examples represents a Shell SM 920.
Bestimmung der Scherstabilität (Scherstabilitätsindex) PSSI wird nach ASTM D 2603 Ref. B vorgenommen. Determination of Shear Stability (Shear Stability Index) PSSI is made in accordance with ASTM D 2603 ref.
Aus 1 170 g des Methacrylsäureesters eines Gemischs von
C11-C16-Alkanolen (Produkt DOBANOL 25L der Shell AG) und
11,7 g 2-Mercaptoethanol wird eine Mischung hergestellt.
Im 4 l Dreihalskolben mit Ölbadheizung, Säbelrührer,
Innenthermometer, N2-Überleitung und Rückflußkühler werden
14,4 g dieser Monomermischung und 130 g 100 N-Öl vorgelegt
und auf 95 Grad C erwärmt. Nach Zugabe von 1,18 g
tert.-Butylper-2-ethylhexanoat als Initator wird ein
Gemisch aus 1 167,3 g des C11-C18-Methacrylsäureesters und
3,5 g Initiator innerhalb von 3,5 Stunden über eine Pumpe
gleichmäßig zudosiert. 2,5 und 5 Stunden nach Zulaufende
werden jeweils 2,34 g tert-Butylper-2-ethylhexanoat
zugegeben und weitere 12 Stunden bei 95 Grad C gehalten.
Danach wird mit 497,2 g 100 N-Öl verdünnt.
Die aktuelle Viskosität wird zu KV100 = 77,6 cSt bestimmt.
Das Molekulargewicht wir durch SEC bestimmt. MW = 19 000
g/mol.From 1,170 g of the methacrylic acid ester of a mixture of C 11 -C 16 -alkanols (product DOBANOL 25L from Shell AG) and 11.7 g of 2-mercaptoethanol, a mixture is prepared. 14.4 g of this monomer mixture and 130 g of 100 N oil are introduced into the 4 l three-necked flask with oil bath heating, saber stirrer, internal thermometer, N 2 transfer and reflux condenser and heated to 95 ° C. After addition of 1.18 g of tert-butyl per-2-ethylhexanoate as an initiator, a mixture of 1 167.3 g of C 11 -C 18 methacrylic acid ester and 3.5 g of initiator is uniform over 3.5 hours via a pump added. 2.5 and 5 hours after the end of each 2.34 g of tert-butyl per-2-ethylhexanoate are added and maintained at 95 degrees C for a further 12 hours. Then it is diluted with 497.2 g of 100 N oil.
The actual viscosity is determined to be KV100 = 77.6 cSt. The molecular weight is determined by SEC. M W = 19,000 g / mol.
In einem 6 l Dreihalskolben mit elektrischem Heizpilz,
Säbelrührer, Innenthermometer, Lufteinleitung und
Füllkörperkolonne mit reglergesteuertem Dampfteiler wird
ein Gemisch auf 1 760,4 g des Produktes aus a) sowie
1 260 g Methylmethacrylat, 0,06 g 4-Hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl
und 0,23 g
Hydrochinonmonomethylether vorgelegt und unter
Luftdurchleitung zum Rückfluß erwärmt. Nach Abnahme von
118 g Destillat wird 1,15 g Lithiummethoxid zugesetzt und
solange am Rückfluß gehalten, bis die Siedetemperatur auf
65 bis 68 Grad C gefallen ist. Danach wird solange
methanolreiches Destillat (65 - 68 Grad C, ca. 17 g)
abgezogen, bis durch Anstieg der Siedetemperatur auf 100
Grad C ein weitgehender Umsatz angezeigt wird. Nach
Abdestillieren von weiteren 280 g Destillat bei 100 Grad C
wird der Ansatz auf Raumtemperatur abgekühlt und durch
eine Seitz-KS80-Filterschicht klar filtriert. Das
überschüssige Methylmethacrylat wird am Vakuumrotationsverdampfer
entfernt.
Ausbeute: 1 750 g Öllösung des Makromonomeren A-1.In a 6 l three-necked flask with electric heating mushroom, saber stirrer, internal thermometer, air inlet and packed column with regulator-controlled vapor divider, a mixture of 1 760.4 g of the product from a) and 1 260 g of methyl methacrylate, 0.06 g of 4-hydroxy-2.2 , 6,6-tetramethylpiperidine-1-oxyl and 0.23 g of hydroquinone monomethyl ether and heated under air through to reflux. After removing 118 g of distillate, 1.15 g of lithium methoxide is added and refluxed until the boiling point has fallen to 65 to 68 degrees Celsius. Thereafter, as long as methanol-rich distillate (65 - 68 degrees C, about 17 g) withdrawn until a rise in the boiling point to 100 degrees C, a large turnover is displayed. After distilling off a further 280 g of distillate at 100 degrees C, the mixture is cooled to room temperature and filtered through a Seitz KS80 filter layer clear. The excess methyl methacrylate is removed on a vacuum rotary evaporator.
Yield: 1 750 g of oil solution of macromonomer A-1.
Man benutzt dieselbe Apparatur wie unter A-1 (a). Im 6 l-Kolben
werden vorgelegt: 1,396 g 100 N-Öl, 155,1 g
Methacrylsäureester eines Gemischs von C11-C16-Alkanolen
(Produkt DOBANOL 25L) und 4,65 g 2-Mercaptoethanol unter
Stickstoff auf 110 Grad C erwärmt. Nach Zugabe von 1,65 g
tert-Butylper-2-ethylhexanoat wird innerhalb von 3,5
Stunden ein Gemisch aus 2 448,9 g des gleichen
Methacrylsäureesters, 75,3 g 2-Mercaptoethanol und 24,5 g
tert.-Butylper-2-ethylhexanoat kontinuierlich zugepumpt.
45 Minuten und 90 Minuten nach Zulaufende werden jeweils
5,2 g Initiator nachgegeben und der Ansatz für weitere 2
Stunden bei 100 Grad C gehalten. Das Resultat zeigt bei
100 Grad C eine Viskosität von 20,9 cSt.
Ausbeute: 4 038 g.
Aktuelle Viskosität KV 100 = 20,9 cST
Molgewicht (SEC) = 5 500 g/molThe same apparatus as in A-1 (a) is used. The 6 l flask is charged with 1.396 g of 100 N oil, 155.1 g of methacrylic acid ester of a mixture of C 11 -C 16 -alkanols (product DOBANOL 25L) and 4.65 g of 2-mercaptoethanol under nitrogen at 110 ° C. , After addition of 1.65 g of tert-butyl per-2-ethylhexanoate is within 3.5 hours, a mixture of 2 448.9 g of the same methacrylic acid ester, 75.3 g of 2-mercaptoethanol and 24.5 g of tert-butyl per- 2-ethylhexanoate continuously pumped. At 45 minutes and 90 minutes after the end of the feed, 5.2 g of initiator are added in each case and the batch is kept at 100 ° C. for a further 2 hours. The result shows at 100 degrees C a viscosity of 20.9 cSt.
Yield: 4 038 g.
Molecular weight (SEC) = 5 500 g / mol
Dieselbe Apparatur wie in Beispiel A-1a) wird angewendet.
Im 6 l-Kolben werden vorgelegt: 1 396 g 100 N-Öl, 155,1 g
Methacrylsäureester eines Gemischs aus C11-C16-Alkanolen
(Produkt DOBANOL 25L) und 3,10 g 2-Mercaptoethanol und
unter Stickstoff auf 110 Grad C erwärmt. Nach Zugabe von
1,65 g tert.-Butylper-2-ethylhexanoat (Initiator) wird
innerhalb von 3,5 Stunden ein Gemisch aus 2 448,9 g des
gleichen Methacrylsäureesters, 49,0 g 2-Mercaptoethanol
und 24,5 g Initiator kontinuierlich zugepumpt. 45 Minuten
und 90 Minuten nach Zulaufende werden jeweils 5,2 g
Initiator nachgegeben und der Ansatz für weitere 12
Stunden bei 110 Grad C gehalten.
Aktuelle Viskosität KV 100 = 21 cSt
Molgewicht (SEC) = 7 720 g/molThe same apparatus as in Example A-1a) is used. The 6 l flask is charged with: 1.396 g of 100 N oil, 155.1 g of methacrylic acid ester of a mixture of C 11 -C 16 -alkanols (product DOBANOL 25L) and 3.10 g of 2-mercaptoethanol and under nitrogen to 110 ° C heated. After addition of 1.65 g of tert-butyl per-2-ethylhexanoate (initiator) is within 3.5 hours, a mixture of 2 448.9 g of the same methacrylic acid ester, 49.0 g of 2-mercaptoethanol and 24.5 g of initiator continuously pumped. At 45 minutes and 90 minutes after the end of the feed, 5.2 g of initiator are added in each case and the batch is kept at 110 ° C. for a further 12 hours.
Molecular weight (SEC) = 7 720 g / mol
Dieselbe Apparatur wie für Beispiel A-1a). Im 6 l-Kolben
werden vorgelegt: 1 396 g 100 N-Öl, 155,1 g
Methacrylsäureester eines Gemischs von C11-C16-Alkanolen
(Produkt DOBANOL 25L) sowie 1,55 g 2-Mercaptoethanol und
unter Stickstoff auf 110 Grad C erwärmt. Nach Zugabe von
1,65 tert.-Butylper-2-ethylhexanoat wird innerhalb von 3,5
Stunden ein Gemisch aus 2 448,9 g des oben genannten
Methacrylesters, 25,5 g 2-Mercpatoethanol und 24,5 g
tert.-Butylper-2-ethylhexanoat kontinuierlich zugepumpt.
45 Minuten und 90 Minuten nach Zulaufende werden jeweils
5,2 g Butylper-2-ethylhexanoat nachgegeben und der Ansatz
für weitere 12 Stunden bei 110 Grad C gehalten.
Aktuelle Viskosität KV 100 = 52 cSt.
Molgewicht (SEC) = 13 600 g/mol.The same apparatus as for Example A-1a). The 6 l flask is charged with: 1.396 g of 100 N oil, 155.1 g of methacrylic acid ester of a mixture of C 11 -C 16 -alkanols (product DOBANOL 25L) and 1.55 g of 2-mercaptoethanol and under nitrogen to 110 ° C heated. After addition of 1.65 t-butylper-2-ethylhexanoat within 3.5 hours, a mixture of 2 448.9 g of the above methacrylic ester, 25.5 g of 2-mercaptopanol and 24.5 g of tert-butyl per 2-ethylhexanoate continuously pumped. At 45 minutes and 90 minutes after the end of the feed, 5.2 g of butyl per-2-ethylhexanoate are added in each case and the batch is kept at 110 ° C. for a further 12 hours.
Molecular weight (SEC) = 13,600 g / mol.
Verwendet wird eine Apparatur gemäß Beispiel A-1a). Die
Monomermischung wird aus 227,7 g Makromonomer aus Beispiel
A-1, 106,3 g Methacrylsäureester eines Gemischs von C11-C16-Alkanolen
(Produkt DOBANOL 25 L) und 45,5 g
Methylmethacrylat hergestellt, 24,5 g dieser
Monomermischung werden mit 220,5 g 100 N-Öl in der
Apparatur vorgelegt und unter Stickstoff auf 82 Grad C
erwärmt. Nach Zugabe von 0,88 g tert.-Butylper-2-ethylhexanoat
zur Vorlage werden innerhalb von 3,5 Stunden
355 g Monomermischung zusammen mit 0,56 g tert.-Butylper-2-ethylhexanoat
kontinuierlich zugepumpt. Zwölf Stunden
nach Zulaufende werden weitere 0,5 g tert.-Butylper-2-hexanoat
zugegeben und 8 Stunden bei 82 Grad C
nachreagiert. Danach wird durch Zugabe von 150 g 100 N-Öl
verdünnt.
Ausbeute: 600 g Öllösung des Pfropfpolymeren PFP-1.An apparatus according to Example A-1a) is used. The monomer mixture is prepared from 227.7 g of macromonomer from Example A-1, 106.3 g of methacrylic acid ester of a mixture of C 11 -C 16 -alkanols (product DOBANOL 25 L) and 45.5 g of methyl methacrylate, 24.5 g of this monomer mixture are charged with 220.5 g of 100 N oil in the apparatus and heated to 82 degrees C under nitrogen. After addition of 0.88 g of tert-butyl per-2-ethylhexanoate to the original, 355 g of monomer mixture are continuously pumped in over 3.5 hours together with 0.56 g of tert-butyl per-2-ethylhexanoate. Twelve hours after the end of the addition, a further 0.5 g of tert-butyl per-2-hexanoate are added and the reaction is continued at 82 ° C. for 8 hours. It is then diluted by the addition of 150 g of 100 N oil.
Yield: 600 g of oil solution of the graft polymer PFP-1.
Verwendet wird die Apparatur gemäß Beispiel A-1a). Im
Dreihalskolben werden 122,9 g des Makromonomeren aus
Beispiel A-2, 20,0 g 2-(N-Morpholinyl)-ethylmethacrylat
und 0,15 g Dodecylmercaptan vorgelegt und unter Stickstoff
auf 100 Grad C erwärmt und danach 1,0 g tert.-Butylper-2-ethylhexanoat
zugegeben. Nach 3 bzw. 7 Stunden nach der
ersten Initiatorzugabe werden jeweils weitere 0,2 g tert.-Butylper-2-ethylhexanoat
zugegeben und der Ansatz wird
weitere 12 Stunden bei 100 Grad C gehalten.
Ausbeute: : 143 g Öllösung des Kammpolymeren PFP-2.The apparatus according to Example A-1a) is used. 122.9 g of the macromonomer from Example A-2, 20.0 g of 2- (N-morpholinyl) -ethyl methacrylate and 0.15 g of dodecylmercaptan are placed in the three-necked flask and heated to 100 ° C. under nitrogen and then 1.0 g of tert Butylper-2-ethylhexanoate added. After 3 or 7 hours after the first initiator addition, in each case an additional 0.2 g of tert-butyl per-2-ethylhexanoate is added and the batch is kept at 100 ° C. for a further 12 hours.
Yield:: 143 g of oil solution of the comb polymer PFP-2.
Apparatur wie in Beispiel A-1. Im Dreihalskolben werden
122,9 g des Makromonomeren aus Beispiel A-3, 20 g 2-(N-Morpholinyl)-ethylmethacrylat
und 0,15 g Dodecylmercaptan
vorgelegt und unter Stickstoff auf 100 Grad C erwärmt und
danach 1,0 g tert.-Butylper-2-ethylhexanoat zugegeben.
nach 3 bzw. 7 Stunden nach der ersten Initiatorzugabe
werden jeweils weitere 0,2 g Initiator zugegeben und der
Ansatz für weitere 12 Stunden bei 100 Grad C gehalten.
Ausbeute: 143 g Öllösung des Kammpolymeren PFP-3.Apparatus as in Example A-1. 122.9 g of the macromonomer from Example A-3, 20 g of 2- (N-morpholinyl) -ethyl methacrylate and 0.15 g of dodecylmercaptan are placed in the three-necked flask and heated to 100 ° C. under nitrogen and then 1.0 g of tertiary Butylper-2-ethylhexanoate added. After 3 or 7 hours after the first initiator addition, in each case a further 0.2 g of initiator is added and the mixture is kept at 100 ° C. for a further 12 hours.
Yield: 143 g of oil solution of the comb polymer PFP-3.
Apparatur wie in Beispiel A-1. Im Dreihalskolben werden
138,2 g des Makromonomeren aus Beispiel A-4, 10 g 2-(N-Morpholinyl)-ethylmethacrylat
(= Monomer VII-a) und 0,15 g
Dodecylmercaptan vorgelegt und unter Stickstoff auf 100
Grad C erwärmt und danach 1,0 g tert.-Butylper-2-ethylhexanoat
zugegeben. Nach 3 bzw. 7 Stunden nach der
Initiatorzugabe werden jeweils weitere 0,2 g Initiator
zugegeben und der Ansatz für weitere 12 Stunden bei 100
Grad C gehalten.
Ausbeute: 148 g Öllösung des Kammpolymeren PFP-4. Apparatus as in Example A-1. In a three-necked flask, 138.2 g of the macromonomer from Example A-4, 10 g of 2- (N-morpholinyl) -ethyl methacrylate (= monomer VII-a) and 0.15 g of dodecylmercaptan are charged and heated to 100 ° C. under nitrogen and then 1.0 g of tert-butyl per-2-ethylhexanoate was added. After 3 or 7 hours after the initiator addition, in each case a further 0.2 g of initiator is added and the mixture is kept at 100 ° C. for a further 12 hours.
Yield: 148 g of oil solution of the comb polymer PFP-4.
Apparatur wie in Beispiel A-1. Im Dreihalskolben werden
138,2 g des Makromonomeren gemäß Beispiel A-2, 5,0 g 2-(N-Morpholinyl)-ethylmethacrylat,
5,0 g N-Vinylpyrrolidon (=
Monomer VIII-a) und 0,15 g Dodecylmercaptan vorgelegt und
unter Stickstoff auf 100 Grad C erwärmt und danach 1,0 g
tert.-Butyl-2-ethylhexanoat zugegeben. 3 bzw. 7 Stunden
nach der ersten Initiatorzugabe werden jeweils weitere
0,2 g tert.-Butylper-2-ethylhexanoat zugegeben und der
Ansatz für weitere 12 Stunden bei 100 Grad C gehalten.
Ausbeute: 148 g Öllösung des Kammpolymeren PFP-5.Apparatus as in Example A-1. The three-necked flask is charged with 138.2 g of the macromonomer according to Example A-2, 5.0 g of 2- (N-morpholinyl) -ethyl methacrylate, 5.0 g of N-vinylpyrrolidone (= monomer VIII-a) and 0.15 g of dodecylmercaptan and heated under nitrogen to 100 degrees C and then added 1.0 g of tert-butyl 2-ethylhexanoate. 3 or 7 hours after the first initiator addition, in each case a further 0.2 g of tert-butyl per-2-ethylhexanoate is added and the batch is kept at 100 ° C. for a further 12 hours.
Yield: 148 g of oil solution of the comb polymer PFP-5.
Verwendet wird eine Apparatur gemäß Beispiel A-1a). Die
Monomermischung wird aus 299,5 g Makromonomer aus Beispiel
A-1, 65 g Methacrylsäureester eines Gemisches von C11 bis
C16-Alkanolen (Produkt Dobanol 25 L), 65,0 g
Methylmethacrylat und 70,5 g 100 N-Öl hergestellt, 50 g
dieser Monomermischung werden in der Apparatur vorgelegt
und unter Stickstoff auf 90 Grad C erwärmt. Nach Zugabe
von 0,06 g tert.-Butylper-2-ethylhexanoat zur Vorlage
werden innerhalb von 3,5 Stunden 450 g der Monomermischung
zusammen mit 0,59 g tert.-Butyl-2-ethylhexanoat
kontinuierlich zugepumpt. 1,5 Stunden nach Zulaufende
werden zur Verdünnung 312,5 g 100 N-Öl zugegeben. 6
Stunden nach Zulaufende werden weitere 0,65 g tert.-Butylper-2-ethylhexanoat
zugegeben und 8 Stunden
nachreagiert.
Ausbeute: 812 g Öllösung des Pfropfcopolymeren PFP-6. An apparatus according to Example A-1a) is used. The monomer mixture is prepared from 299.5 g of macromonomer from Example A-1, 65 g of methacrylic acid ester of a mixture of C 11 to C 16 -alkanols (product Dobanol 25 L), 65.0 g of methyl methacrylate and 70.5 g of 100 N oil , 50 g of this monomer mixture are placed in the apparatus and heated to 90 degrees C under nitrogen. After addition of 0.06 g of tert-butyl per-2-ethylhexanoate to the template, 450 g of the monomer mixture are continuously pumped in over 3.5 hours together with 0.59 g of tert-butyl 2-ethylhexanoate. 1.5 hours after the end of the feed, 312.5 g of 100 N oil are added for dilution. 6 hours after the end of the feed, a further 0.65 g of tert-butyl per-2-ethylhexanoate are added and the reaction is continued for 8 hours.
Yield: 812 g of oil solution of the graft copolymer PFP-6.
Verwendet wird eine Apparatur gemäß Beispiel A-1a). die
Monomermischung wird aus 276,5 g Makromonomer aus Beispiel
A-1, 120,0 g n-Butylmethacrylat und 103,5 g 100 N-Öl
hergestellt. 75 g dieser Monomermischung werden in der
Apparatur vorgelegt und unter Stickstoff auf 90 Grad C
erwärmt. Nach Zugabe von 0,09 g tert.-Butylper-2-ethylhexanoat
zur Vorlage werden innerhalb von 3,5 Stunden
425 g der Monomermischung zusammen mit 0,51 g tert.-Butylper-2-ethylhexanoat
kontinuierlich zugepumpt. 6
Stunden nach Zulaufende werden weitere 0,6 g ter.-Butylper-2-ethylhexanoat
zugegeben und 8 Stunden
nachreagiert. Danach wird durch Zugabe von 100 g 100 N-Öl
verdünnt.
Ausbeute: 600 g Öllösung des Pfropfcopolymeren PFP-7.An apparatus according to Example A-1a) is used. the monomer mixture is prepared from 276.5 g macromonomer from Example A-1, 120.0 g n-butyl methacrylate and 103.5 g 100 N oil. 75 g of this monomer mixture are placed in the apparatus and heated to 90 degrees C under nitrogen. After addition of 0.09 g of tert-butyl per-2-ethylhexanoate for submission, 425 g of the monomer mixture are continuously pumped in over 3.5 hours together with 0.51 g of tert-butyl per-2-ethylhexanoate. 6 hours after the end of the addition, a further 0.6 g of tert-butyl per-2-ethylhexanoate are added and the reaction is continued for 8 hours. It is then diluted by adding 100 g of 100 N oil.
Yield: 600 g of oil solution of the graft copolymer PFP-7.
Verwendet wird eine Apparatur gemäß Beispiel A-1a). Die
Monomermischung wird aus 207,4 g Makromonomer aus Beispiel
A-1, 165,0 g n-Butylmethacrylat und 127,6 g 100 N-Öl
hergestellt. 75 g dieser Monomermischung werden in der
Apparatur vorgelegt und unter Stickstoff auf 85 Grad C
erwärmt. Nach Zugabe von 0,09 g tert.-Butylper-2-ethylhexanoat
zur Vorlage werden innerhalb von 3,5 Stunden
425 g der Monomermischung zusammen mit 0,51 g tert.-Butylper-2-ethylhexanoat
kontinuierlisch zugepumpt. 1,5
Stunden nach Zulaufende werden zur Verdünnung 250 g
100 N-Öl zugegeben. 6 Stunden nach Zulaufende werden
weitere 0,6 g tert.-Butylper-2-ethylhexanoat zugegeben und
8 Stunden nachreagiert. Danach werden zur weiteren
Verdünnung 450 g 100 N-Öl zugegeben.
Ausbeute: 1 200 g Öllösung des Pfropfcopolymeren PFP-8.An apparatus according to Example A-1a) is used. The monomer mixture is prepared from 207.4 g macromonomer from Example A-1, 165.0 g n-butyl methacrylate and 127.6 g 100 N oil. 75 g of this monomer mixture are introduced into the apparatus and heated to 85 ° C. under nitrogen. After addition of 0.09 g of tert-butyl per-2-ethylhexanoate for submission, 425 g of the monomer mixture are continuously pumped in over 3.5 hours together with 0.51 g of tert-butyl per-2-ethylhexanoate. 1.5 hours after the end of the feed, 250 g of 100 N oil are added for dilution. 6 hours after the end of the addition, a further 0.6 g of tert-butyl per-2-ethylhexanoate are added and the reaction is continued for 8 hours. Thereafter, 450 g of 100 N oil are added for further dilution.
Yield: 1,200 g of oil solution of the graft copolymer PFP-8.
Zur Prüfung der Emulgatorwirkung der Pfropfpolymere kann der im folgenden angegebene Toluol-Wasser-Emulgiertest zur Prüfung der Dispergierwirkung der Ruß-Tüpfeltest angewendet werden.For testing the emulsifier effect of Graft polymers may be the following toluene-water emulsified test for testing the dispersing effect of Soot-spot test can be applied.
Durchführung des Toluol/Wasser-Emulgiertests:
Das auf seine Emulgierwirkung zu prüfende Additiv wird in
Toluol (versetzt mit 20 ppm Oracetblau B) mit einer
Polymerkonzentration von 1 Gew.-% gelöst. In ein
graduiertes 20 ml Schliffreagenzglas werden nacheinander 7
ml des. Wasser und 13 ml der 1 %igen Toluollösung
eingefüllt und 15 Minuten im Wasserbad bei 30 Grad C
temperiert. Durch heftiges Schütteln des Reagenzglases
wird eine gleichförmige Emulsion erzeugt und die Probe in
das Temperierbad zurückgestellt. Das Auftrennen der
Emulsion in die Schichten Toluol, Emulsion und Wasser wird
über einen Zeitraum von 24 Stunden beobachtet. Hierzu wird
zu den Zeiten 5 Minuten, 10 Minuten, 100 Minuten und 24
Stunden die Schichtgrenze Toluol/Emulsion sowie die
Schichtgrenze Emulsion/Wasser anhand der Graduierung
abgelesen (s. Abb. 1a). Carrying out the toluene / water emulsification test:
The additive to be tested for its emulsifying effect is described in
Toluene (added with 20 ppm Oracet Blue B) with a
Polymer concentration of 1 wt .-% dissolved. In one
graduated 20 ml grinding test tube are successively 7
ml of water and 13 ml of the 1% toluene solution
filled and 15 minutes in a water bath at 30 degrees C.
tempered. By vigorously shaking the test tube
a uniform emulsion is produced and the sample in
reset the tempering bath. The separation of the
Emulsion is added to the layers of toluene, emulsion and water
observed over a period of 24 hours. For this purpose is
at the
Die Quantifizierung der Emulgierwirkung in %-Werten
erfolgt nach dem in Abb. 1b gezeigten Schema. Hierbei wird
der Anteil der im Beobachtungszeitraum 5 Minuten bis 24
Stunden vorliegenden Emulsion durch das Verhältnis der
Fläche A zur Gesamtfläche A + B charakterisiert und in %-Werten
angegeben.The quantification of the emulsifying effect in% values
takes place according to the scheme shown in Fig. 1b. This is
the proportion of the
Mit dem zu prüfenden Additiv werden in 150 N-Öl (Enerpar 11) zwei Stammlösungen aufgemischt: Stammlösung I mit 0,375 % Polymergehalt und Stammlösung II mit 0,75 % Polymergehalt. Von jeder Stammlösung werden 2 Rußdispersionslösungen angesetzt (Doppelbestimmung). Hierzu werden jeweils in ein 150 ml Becherglas 1,5 g Ruß (Flammruß, Degussa Spezialschwarz 4) und 50 g Stammlösung eingewogen und danach mit einem Ultra-Turrax Intensivrührer 30 Minuten bei 9 000 u/Minute aufgerührt. Danach werden von jeder Dispersionslösung 20 µl auf Filterpapier (Papier Durieux 122) getüpfelt. Nach 48 Stunden ebener Lagerung bei 30 Grad C werden die Tüpfelflecken ausgewertet. Hierzu wird der Durchmesser des Rußfleckens und der Durchmesser des ihn umgebenden Ölfleckens ausgemessen und deren Verhältnis in % angegeben: The additive to be tested is dissolved in 150 N oil (Enerpar 11) mixed two stock solutions: stock solution I with 0.375% polymer content and stock solution II with 0.75% Polymer content. From each stock solution become 2 Soot dispersion solutions prepared (double determination). For this purpose, in each case in a 150 ml beaker 1.5 g of carbon black (Flame black, Degussa special black 4) and 50 g stock solution weighed and then with an Ultra-Turrax Intensive stirrer stirred for 30 minutes at 9,000 u / minute. Thereafter, 20 μl of each dispersion solution Filter paper (paper Durieux 122) spotted. After 48 Hours of even storage at 30 degrees C will be the Punctuated flecks evaluated. For this, the diameter of the Soot stain and the diameter of the surrounding it Oil spill measured and their ratio in% stated:
Durchmesser Rußfleck/Durchmesser Ölfleck * 100 %.
Die Gesamtbewertung des Tüpfeltests ergibt sich als Summe
der vier prozentualen Einzelbewertungen. Produkte mit
schlechter Rußdispergierung ergeben Gesamtbewertungen von
ca. 70 % und niedriger, Produkte mit guter
Rußdispergierung ergeben Gesamtbewertungen von ≥ 130 %.
Soot spot / diameter oil spot diameter * 100%.
The total score of the spot test is the sum of the four percentage ratings. Products with poor soot dispersion give overall ratings of about 70% and lower, products with good carbon black dispersion give overall ratings of ≥ 130%.
Claims (4)
- Use of graft polymers PFP which are synthesised froma) 10-90 wt.%, based on PFP, of polyalkylmethacrylate macromonomers (A) which are copolymerised withb) 0-90 wt.%, based on PFP, of alkyl (meth)acrylic acid esters (AMA) with C6-30 alkyl groups and withc) 0-60 wt.%, based on PFP, of non-functionalised comonomers (B) selected from the group consisting of alkyl (meth)acrylic acid esters having C1-5 alkyl groups, styrene, alkyl styrenes having C1-4 alkyl groups and fatty acid vinyl esters having 2-12 carbon atoms in the fatty acid group and withd) 0-40 wt.%, based on PFP, of functionalised comonomers (C) selected from the group consisting of functionalised (meth)acrylic acid esters and amides and the vinyl heterocyclic groups,
in a carrier medium TM, as lubricant additives with the effect of improving the viscosity index. - Use according to claim 1, characterised in that the polyalkyl methacrylate macromonomers (A) are compounds of formula II wherein
- x =
- biradical group
- R1 =
- -H or -CH3
- R2 =
- -H or -CH3
- n =
- 6 to 30
- p =
- average degree of polymerisation of the macromonomer
- Use according to claims 1 and 2, characterised in that the weight-average molecular weight of the graft polymers PFP is in the range from 5000 to 1,000,000.
- Use according to claim 1 containing as graft polymers the graft polymers PFP' which are synthesised froma) 10-90 % by weight of polyfunctionalised polyalkyl methacrylate macromonomers (A'), containinga1) 0-90 wt.% of alkyl (meth)acrylic ester (AMA') having C6-30 alkyl groupsa2) 0-40 wt.% of non-functionalised comonomers (B') from the group consisting of alkyl (meth)acrylic acid esters having C1-5 alkyl groups, styrene, alkyl styrenes having C1-4 alkyl groups and fatty acid vinyl esters having 2-12 carbon atoms in the fatty acid group, anda3) 0-100 wt.% of functionalised comonomers (C') selected from the group consisting of functionalised (meth)acrylic acid esters and amides and the vinyl heterocycles,b) 0-90 wt.% of monomers selected from the group consisting of alkyl (meth)acrylic acid esters (AMA) with C6-30 alkyl groups,c) 0-60 wt.% of monomers (B) selected from the group consisting of alkyl (meth)acrylic acid esters having C1-5 alkyl groups, styrene, alkyl styrenes having C1-4 alkyl groups and fatty acid vinyl esters having 2-12 carbon atoms in the fatty acid group,d) 0-40 wt.% of functionalised comonomers (C) selected from the group consisting of functionalised (meth)acrylic acid esters and amides and the vinyl heterocyclic groups, with the proviso that the sum of the copolymerised monomers (AMA), (B) and (C) make up 10-90 wt.%, based on PFP'.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19518786 | 1995-05-22 | ||
DE19518786A DE19518786A1 (en) | 1995-05-22 | 1995-05-22 | Lubricant additives |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0744457A2 EP0744457A2 (en) | 1996-11-27 |
EP0744457A3 EP0744457A3 (en) | 1997-09-24 |
EP0744457B1 true EP0744457B1 (en) | 2003-09-24 |
Family
ID=7762590
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96107578A Expired - Lifetime EP0744457B1 (en) | 1995-05-22 | 1996-05-13 | Lubricant additive |
Country Status (6)
Country | Link |
---|---|
US (1) | US5756433A (en) |
EP (1) | EP0744457B1 (en) |
JP (2) | JP4142121B2 (en) |
AT (1) | ATE250659T1 (en) |
DE (2) | DE19518786A1 (en) |
SG (1) | SG54334A1 (en) |
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US11365273B2 (en) | 2019-12-16 | 2022-06-21 | Infineum International Limited | High viscosity index comb polymer viscosity modifiers and methods of modifying lubricant viscosity using same |
US11384311B2 (en) | 2019-12-16 | 2022-07-12 | Infineum International Limited | High viscosity index comb polymer viscosity modifiers and methods of modifying lubricant viscosity using same |
US11685874B2 (en) | 2019-12-16 | 2023-06-27 | Infineum International Limited | High viscosity index comb polymer viscosity modifiers and methods of modifying lubricant viscosity using same |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19518786A1 (en) * | 1995-05-22 | 1996-11-28 | Roehm Gmbh | Lubricant additives |
US5955405A (en) * | 1998-08-10 | 1999-09-21 | Ethyl Corporation | (Meth) acrylate copolymers having excellent low temperature properties |
US6495618B1 (en) | 1999-12-17 | 2002-12-17 | E. I. Du Pont De Nemours And Company | Graft copolymer with an amide functional group as a pigment dispersant |
US6642189B2 (en) | 1999-12-22 | 2003-11-04 | Nippon Mitsubishi Oil Corporation | Engine oil compositions |
US6323164B1 (en) * | 2000-11-01 | 2001-11-27 | Ethyl Corporation | Dispersant (meth) acrylate copolymers having excellent low temperature properties |
US6746993B2 (en) * | 2001-04-06 | 2004-06-08 | Sanyo Chemical Industries, Ltd. | Viscosity index improver and lube oil containing the same |
DE102005015931A1 (en) * | 2005-04-06 | 2006-10-12 | Rohmax Additives Gmbh | Polyalkyl (meth) acrylate copolymers with excellent properties |
US20070117725A1 (en) * | 2005-11-22 | 2007-05-24 | Shih-Ying Hsu | Acrylic synthetic lubricant |
DE102009001446A1 (en) * | 2009-03-10 | 2010-09-23 | Evonik Rohmax Additives Gmbh | Use of comb polymers as antifatigue additives |
US8143201B2 (en) * | 2010-03-09 | 2012-03-27 | Infineum International Limited | Morpholine derivatives as ashless TBN sources and lubricating oil compositions containing same |
JP2012188583A (en) * | 2011-03-11 | 2012-10-04 | Sanyo Chem Ind Ltd | Viscosity index-improving agent and lubricant composition |
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JP2013147608A (en) * | 2012-01-23 | 2013-08-01 | Sanyo Chem Ind Ltd | Viscosity index improving agent, and lubricating oil composition |
JP2014080537A (en) * | 2012-10-18 | 2014-05-08 | Sanyo Chem Ind Ltd | Viscosity index improver and lubricating oil composition |
WO2016152679A1 (en) * | 2015-03-20 | 2016-09-29 | 出光興産株式会社 | Viscosity index improver, lubricant composition and method for producing lubricant composition |
EP3455266B1 (en) | 2016-05-13 | 2020-10-28 | Evonik Operations GmbH | Graft copolymers based on polyolefin backbone and methacrylate side chains |
KR101816427B1 (en) * | 2016-08-01 | 2018-01-08 | 현대자동차주식회사 | Composition of continuously variable transmission oil for improving fuel efficiency and endurance performance |
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MX2019007208A (en) * | 2016-12-19 | 2019-08-16 | Evonik Oil Additives Gmbh | Lubricating oil composition comprising dispersant comb polymers. |
KR102587267B1 (en) * | 2018-01-23 | 2023-10-11 | 에보닉 오퍼레이션스 게엠베하 | Polymer-inorganic nanoparticle compositions, methods for their preparation and their use as lubricant additives |
KR20220158221A (en) * | 2020-03-25 | 2022-11-30 | 도요보 가부시키가이샤 | polyamide resin composition |
WO2024053735A1 (en) * | 2022-09-09 | 2024-03-14 | 三菱ケミカル株式会社 | Polymer, friction reducer for lubricating oil, and lubricating oil composition |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0728780A2 (en) * | 1995-02-24 | 1996-08-28 | Röhm Gmbh | Graftpolymers with emulgator properties |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1053529A (en) * | ||||
US3304260A (en) * | 1960-12-30 | 1967-02-14 | Monsanto Co | Compositions of improved viscosity index containing alkyl polymethacrylate of high relative syndiotacticity |
DE3607444A1 (en) * | 1986-03-07 | 1987-09-10 | Roehm Gmbh | ADDITIVES FOR MINERAL OILS WITH IMPROVEMENT EFFECT |
JPS62220593A (en) * | 1986-03-20 | 1987-09-28 | Kao Corp | Viscosity index improver for lubricant |
US4985160A (en) * | 1989-02-08 | 1991-01-15 | E. I. Du Pont De Nemours And Company | Branched polymers as fuel oil additives |
DE3930142A1 (en) * | 1989-09-09 | 1991-03-21 | Roehm Gmbh | DISPERGING VISCOSITY INDEX IMPROVERS |
DE4121811A1 (en) * | 1991-07-02 | 1993-01-07 | Roehm Gmbh | METHOD FOR PRODUCING POLYALKYL METHACRYLATE MACROMONOMERS AND THE USE THEREOF FOR PRODUCING COMB POLYMERS |
DE4309853A1 (en) * | 1993-03-26 | 1994-09-29 | Roehm Gmbh | Thermoplastic processable elastomers with improved optical properties |
DE4312715A1 (en) * | 1993-04-20 | 1994-10-27 | Roehm Gmbh | Comb polymers |
US5312884A (en) * | 1993-04-30 | 1994-05-17 | Rohm And Haas Company | Copolymer useful as a pour point depressant for a lubricating oil |
JP2748104B2 (en) * | 1994-03-08 | 1998-05-06 | 三洋化成工業株式会社 | Viscosity index improver and lubricating oil |
DE19518786A1 (en) * | 1995-05-22 | 1996-11-28 | Roehm Gmbh | Lubricant additives |
-
1995
- 1995-05-22 DE DE19518786A patent/DE19518786A1/en not_active Withdrawn
-
1996
- 1996-05-13 EP EP96107578A patent/EP0744457B1/en not_active Expired - Lifetime
- 1996-05-13 DE DE59610726T patent/DE59610726D1/en not_active Expired - Lifetime
- 1996-05-13 AT AT96107578T patent/ATE250659T1/en not_active IP Right Cessation
- 1996-05-15 JP JP12056996A patent/JP4142121B2/en not_active Expired - Fee Related
- 1996-05-20 SG SG1996009837A patent/SG54334A1/en unknown
- 1996-05-22 US US08/652,276 patent/US5756433A/en not_active Expired - Lifetime
-
2008
- 2008-04-09 JP JP2008101040A patent/JP2008255359A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0728780A2 (en) * | 1995-02-24 | 1996-08-28 | Röhm Gmbh | Graftpolymers with emulgator properties |
Non-Patent Citations (1)
Title |
---|
Die Makromolekulare Chemie: Macromolecular Symposia, Band 64 (Dezember 1992), Seiten 85-111 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11365273B2 (en) | 2019-12-16 | 2022-06-21 | Infineum International Limited | High viscosity index comb polymer viscosity modifiers and methods of modifying lubricant viscosity using same |
US11384311B2 (en) | 2019-12-16 | 2022-07-12 | Infineum International Limited | High viscosity index comb polymer viscosity modifiers and methods of modifying lubricant viscosity using same |
US11685874B2 (en) | 2019-12-16 | 2023-06-27 | Infineum International Limited | High viscosity index comb polymer viscosity modifiers and methods of modifying lubricant viscosity using same |
Also Published As
Publication number | Publication date |
---|---|
JP2008255359A (en) | 2008-10-23 |
EP0744457A2 (en) | 1996-11-27 |
ATE250659T1 (en) | 2003-10-15 |
US5756433A (en) | 1998-05-26 |
JPH08311133A (en) | 1996-11-26 |
DE59610726D1 (en) | 2003-10-30 |
JP4142121B2 (en) | 2008-08-27 |
SG54334A1 (en) | 1998-11-16 |
DE19518786A1 (en) | 1996-11-28 |
EP0744457A3 (en) | 1997-09-24 |
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