CH380711A - Process for making a polyester - Google Patents
Process for making a polyesterInfo
- Publication number
- CH380711A CH380711A CH6299058A CH6299058A CH380711A CH 380711 A CH380711 A CH 380711A CH 6299058 A CH6299058 A CH 6299058A CH 6299058 A CH6299058 A CH 6299058A CH 380711 A CH380711 A CH 380711A
- Authority
- CH
- Switzerland
- Prior art keywords
- formula
- component
- polyester
- carbon atoms
- groups
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims description 16
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- -1 aliphatic diester Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SZKKRCSOSQAJDE-UHFFFAOYSA-N Schradan Chemical group CN(C)P(=O)(N(C)C)OP(=O)(N(C)C)N(C)C SZKKRCSOSQAJDE-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- VNTXONBESJNLBI-UHFFFAOYSA-N dinonyl decanedioate Chemical compound CCCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCCC VNTXONBESJNLBI-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
- C10M2207/304—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/102—Polyesters
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
-
- 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
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/108—Phenothiazine
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/12—Gas-turbines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/12—Gas-turbines
- C10N2040/13—Aircraft turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung eines Polyesters
Es ist schon vorgeschlagen worden, zum Schmieren von Gasturbinen Gemische zu verwenden, welche Polyester der Formel ROOCR1COO(R.2OOCR1COO)nR (I) enhalten, worin R Reste von einwertigen Alkoholen ROH, Rl Reste von Dikarbonsäuren HOOCR1COOH, R, Reste von Glykolen HOR2OH sind und n eine Zahl von 1 bis 6 ist, die nicht notwendigerweise eine ganze Zahl sein muss, und die, wenn sie gebrochen ist, anzeigt, dass es sich um eine Mischung handelt.
Von einem Schmiermittelgemisch, welches zum Schmieren von Gasturbinen benützt wird, wird angenommen, dass es im wesentlichen aus 40 Vol.O/o Dinonylsebacat und 60 Vol.0/o eines Polyesters der Formel I, in welcher n gleich 1 oder angenähert 1 ist, besteht, wobei der Polyester aus 2-Äthylhexanol, Sebazinsäure und Polyglykol 200 (hauptsächlich Tetraäthylenglykol) hergestellt ist. Schmiermittel dieses Typs leiden unter gewissen Nachteilen, deren wichtigster ist, dass ihre Tieftemperatur-Eigenschaften infolge der Tendenz des Polyesters zum Auskristallisieren nicht vollständig befriedigen.
In einem anderen Patent sind Schmiermittelgemische beschrieben, welche einen Diester und einen Polyester enthalten, und in welchen der Diester ein flüssiger aliphatischer Diester einer gesättigten aliphatischen Dikarbonsäure und der Polyester einer der Formel list, in welcher R der Rest eines aliphatischen einwertigen Alkohols ROH, R1 der Rest einer aliphatischen oder aromatischen Dikarbonsäure HOOCRtCOOH, R, der Rest eines Glykols oder Polyglykols HOR2OH und n eine Zahl grösser als 1 ist.
Es ist in den meisten Fällen möglich, in solchen Gemischen, wenn sie zum Schmieren von Gasturbinen verwendet werden, einen grösseren Anteil an Diester zu verwenden, aber selbst dann sind die Tieftemperatur-Eigenschaften solcher Gemische nicht vollständig zufriedenstellend, und, um ein Gemisch zu erzeugen, welches sowohl den Viskositätsanforderungen für Hoch- als auch Tieftemperatur der britischen Vorschrift für Gasturbinen Schmiermittel (DERD 2487) genügt, war es bis anhin notwendig, im Gemisch eine kleine Menge eines die Kristallisation unterdrückenden Mittels, wie z. B. eines Polymers eines Alkylesters der Akryl oder Methakrylsäure, beispielsweise des Polymers, welches unter der markenrechtlich geschützten Bezeichnung ACRYLOID HF 825 verkauft wird, und das ein polymerisierter höherer Alkylester von Methakrylsäure ist, aufzulösen.
Solche Polymere wirken kristallisationsverhütend bei niedrigen Temperaturen, beispielsweise dem Stockpunkt, und verbessern den Viskositätsindex der Gemische, welchen sie beigemischt werden, aber unglücklicherweise haben sie eine gegenteilige Wirkung auf die Scherbeständigkeit der Gemische.
Es wurde nun gefunden, dass gewisse Polyester, die früher nicht beschrieben wurden, Eigenschaften aufweisen, welche sie besonders geeignet als synthetische Gasturbinen-Schmiermittel und Weichmacher oder als Bestandteile von solchen machen. Im allgemeinen war man beim Gebrauch dieser neuen Polyester in der Lage, synthetische Gasturbinen-Schmiermittel zu erzeugen, welche eine hervorragende thermische Stabilität und bessere Tieftemperatur-Eigenschaften besitzen als die früher hergestellten Schmiermittel für den gleichen Zweck.
Die Erfindung betrifft ein Verfahren zur Herstellung eines Polyesters, der Moleküle der Formel ROOCRjCOO(R2OOCR1COO)R enthält, in welcher n eine ganze Zahl grösser als Null, R Alkylgruppen mit 4 bis 18 Kohlenstoffatomen, R1 Alkylengruppen mit 4 bis 14 Kohlenstoffatomen und R2 Tricyclodecandimethylol-Reste der Formel
EMI2.1
bedeuten, welches Verfahren dadurch gekennzeichnet ist, dass man a) mindestens eine Säure der Formel HOOCR1COOH, in der R1 die angegebene Bedeutung hat, oder, sofern ein solches existiert, deren Anhydrid, mit b) mindestens einem Alkanol der Formel ROH, in der R die angegebene Bedeutung hat, und mit c) mindestens einem der drei isomeren Tricyclodecandimethylole der Formel HO-R2-OH, in der R2 die angegebene Bedeutung hat, umsetzt, wobei man pro Mol der Komponente b)
mindestens l/ó Mol der Komponente c) verwendet und das Mengenverhältnis zwischen der Komponente a) einerseits und den Komponenten b) und c) anderseits so wählt, dass mehr alkoholische Hydroxylgruppen vorhanden sind, als zur vollständigen Veresterung der Komponente a) theoretisch erforderlich sind.
Die Alkyl- und Alkylengruppen, welche im Polyestermolekül vorhanden sind, können geradkettig oder verzweigt sein.
Gemische von gewissen aliphatischen Diestern gesättigter aliphatischer Dikarbonsäuren mit erfindungsgemäss hergestellten Polyestern sind im britischen Patent Nr. 847 593 beschrieben. Besonders geeignete Polyester für diese Zwecke sind solche, welche bei 25o C eine Viskosität von wenigstens 35 000, vorteilhafterweise von wenigstens 50 000 Centistokes besitzen, besonders diejenigen, in welchen die Gruppen R5 7 oder 8 Kohlenstoffatome haben und vorzugsweise Octamethylgruppen sind, und die R 2-Athyl- hexylradikale sind.
Es ist zu verstehen, dass verschiedene R-Gruppen, verschiedene Gruppen und verschiedene R2-Gruppen in einem gegebenen Polyestermolekül vorhanden sein können, und dass die Polyester aus einer Mischung verschiedener Moleküle bestehen können.
Zum Beispiel können die Moleküle verschiedene Werte von n aufweisen. Bei solchen Mischungen wird der Mittelwert von n selbstverständlich nicht notwendigerweise eine ganze Zahl sein. Deshalb ist es nicht erforderlich, dass bei der Herstellung einer Polyestermischung die Ausgangsstoffe, welche zur Reaktion gebracht werden, in einem ganzzahligen Molverhältnis gegenwärtig sind.
Beispiele geeigneter Alkanole, welche bei der Herstellung der Polyester verwendet werden können, sind 2-Athylhexylalkohol, 2-Äthylbutylalkohol, Cetylalkohol, Neopentylalkohol, Trimethylhexilalkohol und Trimethylnonylalkohol. Als am zufriedenstellendsten von diesen Alkoholen wurde 2-Äthylhexylalkohol befunden.
Beispiele geeigneter Säuren sind Sebazinsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Brassylsäure. Als am besten geeignet von diesen Säuren wurde Sebazinsäure befunden.
Beispielsweise wurde ein Polyester (P141) gemäss der Erfindung aus folgenden Ausgangsstoffen hergestellt:
Sebazinsäure 0,5 Mol 2-aithylhexylalkohol 0,05 Mol handelsübliches
Tricyclodecandimethylol 0,55 Mol
Das handelsübliche Tricyclodecandimethylol ist eine Mischung der drei Isomeren
EMI2.2
Die Ausgangsstoffe liess man in einem Dreihals- kolben von 500 ml Fassungsvermögen reagieren, welcher mit einem Rührwerk ausgerüstet war und ein Stickstoffeinlassrohr und einen vertikalen, dampfbeheizten Kondensator, welcher an einen wassergekühlten, abwärts gerichteten Kondensator angeschlossen war, besass.
Stickstoff wurde in einer Menge von angenähert 5 1/Stunde durchgeblasen und der folgende Heizzyklus, bei welchem alle Temperaturen im Innern gemessen wurden, durchgeführt:
Der Inhalt des Kolbens wurde rasch auf 130"C erhitzt, auf welcher Temperatur er während 4 Stunden gehalten wurde. Nachdem die Reaktion bei Temperaturen von 150, 180 und 2000 C während je zweier Stunden fortgesetzt wurde, wurde das Destillat gesammelt, und die obere, aus 2-i2ithylhexylalkohol bestehende Schicht wurde in den Kolben zurückgegossen. Der Diolgehalt der unteren Schicht wurde aus einer Brechungsindexbestimmung errechnet, und nachdem diese Menge dem Kolben wieder zugeführt worden war, wurde eine Aufheizung auf 2400 C vorgenommen, bis der Säurewert unter 5 mg KOHjg fiel.
Bei diesem Stand wurde der Druck auf 17 mm Hg erniedrigt und die Reaktion bei 2400 C fortgesetzt, bis der Säurewert unter 1 mg KOHig gefallen war.
Process for making a polyester
It has already been proposed to use mixtures for lubricating gas turbines which contain polyesters of the formula ROOCR1COO (R.2OOCR1COO) nR (I), in which R is residues of monohydric alcohols ROH, Rl is residues of dicarboxylic acids HOOCR1COOH, R, residues of glycols HOR2OH and n is a number from 1 to 6, which need not necessarily be an integer, and which, when broken, indicates that it is a mixture.
A lubricant mixture which is used to lubricate gas turbines is assumed to consist essentially of 40% by volume of dinonyl sebacate and 60% by volume of a polyester of the formula I, in which n is equal to 1 or approximately 1, consists, the polyester from 2-ethylhexanol, sebacic acid and polyglycol 200 (mainly tetraethylene glycol) is made. Lubricants of this type suffer from certain disadvantages, the most important of which is that their low temperature properties are not entirely satisfactory due to the tendency of the polyester to crystallize out.
Another patent describes lubricant mixtures which contain a diester and a polyester, and in which the diester is a liquid aliphatic diester of a saturated aliphatic dicarboxylic acid and the polyester is one of the formula, in which R is the residue of an aliphatic monohydric alcohol ROH, R1 is the The remainder of an aliphatic or aromatic dicarboxylic acid HOOCRtCOOH, R, the remainder of a glycol or polyglycol HOR2OH and n is a number greater than 1.
It is possible in most cases to use a larger proportion of diester in such mixtures when used to lubricate gas turbines, but even then the low temperature properties of such mixtures are not entirely satisfactory and to produce a mixture , which meets both the viscosity requirements for high and low temperatures of the British regulation for gas turbine lubricants (DERD 2487), it was previously necessary to mix a small amount of a crystallization-suppressing agent, such as. B. a polymer of an alkyl ester of acrylic or methacrylic acid, for example the polymer which is sold under the trademark ACRYLOID HF 825, and which is a polymerized higher alkyl ester of methacrylic acid.
Such polymers have an anti-crystallization effect at low temperatures, e.g. the pour point, and improve the viscosity index of the mixtures to which they are admixed, but unfortunately they have an adverse effect on the shear resistance of the mixtures.
It has now been found that certain polyesters, not previously described, have properties which make them particularly useful as, or constituents of, synthetic gas turbine lubricants and plasticizers. In general, the use of these new polyesters has been able to produce synthetic gas turbine lubricants which have excellent thermal stability and better low temperature properties than previously made lubricants for the same purpose.
The invention relates to a process for the production of a polyester which contains molecules of the formula ROOCRjCOO (R2OOCR1COO) R, in which n is an integer greater than zero, R is alkyl groups with 4 to 18 carbon atoms, R1 is alkylene groups with 4 to 14 carbon atoms and R2 is tricyclodecanedimethylol Remnants of the formula
EMI2.1
mean which process is characterized in that a) at least one acid of the formula HOOCR1COOH, in which R1 has the meaning given, or, if one exists, its anhydride, with b) at least one alkanol of the formula ROH, in which R has the meaning given, and with c) at least one of the three isomeric tricyclodecanedimethylols of the formula HO-R2-OH, in which R2 has the meaning given, is reacted, with one mole of component b)
at least l / ó mol of component c) is used and the quantitative ratio between component a) on the one hand and components b) and c) on the other hand is selected so that more alcoholic hydroxyl groups are present than are theoretically necessary for complete esterification of component a).
The alkyl and alkylene groups present in the polyester molecule can be straight chain or branched.
Mixtures of certain aliphatic diesters of saturated aliphatic dicarboxylic acids with polyesters prepared in accordance with the invention are described in British Patent No. 847,593. Particularly suitable polyesters for these purposes are those which have a viscosity of at least 35,000, advantageously of at least 50,000 centistokes at 25 ° C., especially those in which the groups R5 have 7 or 8 carbon atoms and are preferably octamethyl groups, and the R 2 -Athyl- hexyl radicals.
It should be understood that different R groups, different groups, and different R2 groups can be present in a given polyester molecule, and that the polyesters can be a mixture of different molecules.
For example, the molecules can have different values of n. In such mixtures, of course, the mean value of n will not necessarily be an integer. It is therefore not necessary for the starting materials which are reacted to be present in an integral molar ratio in the production of a polyester mixture.
Examples of suitable alkanols which can be used in preparing the polyesters are 2-ethylhexyl alcohol, 2-ethylbutyl alcohol, cetyl alcohol, neopentyl alcohol, trimethylhexyl alcohol and trimethylnonyl alcohol. Of these alcohols, 2-ethylhexyl alcohol has been found to be the most satisfactory.
Examples of suitable acids are sebacic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, brassylic acid. The most suitable of these acids has been found to be sebacic acid.
For example, a polyester (P141) according to the invention was produced from the following starting materials:
Sebacic acid 0.5 mole 2-ethylhexyl alcohol 0.05 mole commercially available
Tricyclodecane dimethylol 0.55 mole
The commercially available tricyclodecane dimethylol is a mixture of the three isomers
EMI2.2
The starting materials were allowed to react in a three-necked flask with a capacity of 500 ml, which was equipped with a stirrer and had a nitrogen inlet tube and a vertical, steam-heated condenser which was connected to a water-cooled, downward-facing condenser.
Nitrogen was blown through in an amount of approximately 5 liters / hour and the following heating cycle, in which all temperatures inside were measured, carried out:
The contents of the flask were quickly heated to 130 "C, at which temperature they were held for 4 hours. After the reaction was continued at temperatures of 150, 180 and 2000 C for two hours each, the distillate was collected, and the upper, The 2-i2ithylhexyl alcohol layer was poured back into the flask, the diol content of the lower layer was calculated from a refractive index determination, and after this amount was returned to the flask, it was heated to 2400 ° C. until the acid value fell below 5 mg KOHjg .
At this level the pressure was reduced to 17 mm Hg and the reaction continued at 2400 ° C. until the acid value had fallen below 1 mg KOHig.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB25871/57A GB847592A (en) | 1957-08-16 | 1957-08-16 | New polyesters and their method of preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH380711A true CH380711A (en) | 1964-08-15 |
Family
ID=10234730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH6299058A CH380711A (en) | 1957-08-16 | 1958-08-15 | Process for making a polyester |
Country Status (4)
| Country | Link |
|---|---|
| BE (1) | BE570404A (en) |
| CH (1) | CH380711A (en) |
| FR (1) | FR1211548A (en) |
| GB (1) | GB847592A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102020102162A1 (en) | 2020-01-29 | 2021-07-29 | Oq Chemicals Gmbh | TCD ester for low temperature lubricant applications |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4307002A (en) | 1976-09-16 | 1981-12-22 | Hoechst Aktiengesellschaft | Resin binders and process for preparing them |
| US7468335B2 (en) | 2006-03-31 | 2008-12-23 | Imes Robert H | High-strength meltblown polyester webs |
| ES2809826T3 (en) | 2010-02-12 | 2021-03-05 | Donaldson Co Inc | Liquid filters |
| EP3093056B1 (en) | 2011-08-12 | 2025-07-02 | Donaldson Company, Inc. | Liquid filtration media containing two kinds of fibers |
-
0
- BE BE570404D patent/BE570404A/xx unknown
-
1957
- 1957-08-16 GB GB25871/57A patent/GB847592A/en not_active Expired
-
1958
- 1958-08-14 FR FR1211548D patent/FR1211548A/en not_active Expired
- 1958-08-15 CH CH6299058A patent/CH380711A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102020102162A1 (en) | 2020-01-29 | 2021-07-29 | Oq Chemicals Gmbh | TCD ester for low temperature lubricant applications |
| US11795410B2 (en) | 2020-01-29 | 2023-10-24 | Oq Chemicals Gmbh | TCD-esters for low temperature liquid applications |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1211548A (en) | 1960-03-16 |
| BE570404A (en) | |
| GB847592A (en) | 1960-09-07 |
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