DK149456B - Polyakylenglycol stabiliseret mod molekylnedbrydning og viskositetstab ved hjaelp af et hydroquinonderivat - Google Patents
Polyakylenglycol stabiliseret mod molekylnedbrydning og viskositetstab ved hjaelp af et hydroquinonderivat Download PDFInfo
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- DK149456B DK149456B DK301575AA DK301575A DK149456B DK 149456 B DK149456 B DK 149456B DK 301575A A DK301575A A DK 301575AA DK 301575 A DK301575 A DK 301575A DK 149456 B DK149456 B DK 149456B
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- Prior art keywords
- derivative
- gylolol
- polyakylene
- hydroquinine
- stabilized against
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- LJOQGZACKSYWCH-WZBLMQSHSA-N hydroquinine Chemical class C1=C(OC)C=C2C([C@@H](O)[C@@H]3C[C@@H]4CCN3C[C@@H]4CC)=CC=NC2=C1 LJOQGZACKSYWCH-WZBLMQSHSA-N 0.000 title 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 229920001515 polyalkylene glycol Polymers 0.000 description 12
- -1 aryl hydroquinone class compounds Chemical class 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 5
- VRGODCQYIJMNRO-UHFFFAOYSA-N 1-(1,4-dihydroxy-5-phenylcyclohexa-2,4-dien-1-yl)ethanone Chemical compound C1=CC(C(=O)C)(O)CC(C=2C=CC=CC=2)=C1O VRGODCQYIJMNRO-UHFFFAOYSA-N 0.000 description 4
- TZIZLYJVARWPAN-UHFFFAOYSA-N 4-methoxy-2-phenylcyclohexa-1,5-diene-1,4-diol Chemical compound C1=CC(OC)(O)CC(C=2C=CC=CC=2)=C1O TZIZLYJVARWPAN-UHFFFAOYSA-N 0.000 description 4
- QIQYFBQWHBSQKH-UHFFFAOYSA-N 4-methyl-2-phenylcyclohexa-1,5-diene-1,4-diol Chemical compound C1=CC(C)(O)CC(C=2C=CC=CC=2)=C1O QIQYFBQWHBSQKH-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002432 hydroperoxides Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- RLQZIECDMISZHS-UHFFFAOYSA-N 2-phenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1 RLQZIECDMISZHS-UHFFFAOYSA-N 0.000 description 2
- KTDOEZIJHDJXGJ-UHFFFAOYSA-N 3,6-dioctyl-10h-phenothiazine Chemical compound C1=CC(CCCCCCCC)=C2SC3=CC(CCCCCCCC)=CC=C3NC2=C1 KTDOEZIJHDJXGJ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- ZGBSJEHDTXRSQV-UHFFFAOYSA-N 1,4-dihydroxy-5-phenylcyclohexa-2,4-diene-1-carboxylic acid Chemical compound C1=CC(C(=O)O)(O)CC(C=2C=CC=CC=2)=C1O ZGBSJEHDTXRSQV-UHFFFAOYSA-N 0.000 description 1
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- YLWQMBMLQVNIOT-UHFFFAOYSA-N 2,4-diphenylcyclohexa-1,5-diene-1,4-diol Chemical compound C1(=CC=CC=C1)C1=C(O)C=CC(C1)(O)C1=CC=CC=C1 YLWQMBMLQVNIOT-UHFFFAOYSA-N 0.000 description 1
- BRYRWETXZVMCQQ-UHFFFAOYSA-N 2-chloro-3-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1Cl BRYRWETXZVMCQQ-UHFFFAOYSA-N 0.000 description 1
- VDPOTVDNYMHUMG-UHFFFAOYSA-N 2-naphthalen-2-ylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=C3C=CC=CC3=CC=2)=C1 VDPOTVDNYMHUMG-UHFFFAOYSA-N 0.000 description 1
- XAMIQJRAVLTPTE-UHFFFAOYSA-N 2-nitro-3-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C([N+]([O-])=O)=C1C1=CC=CC=C1 XAMIQJRAVLTPTE-UHFFFAOYSA-N 0.000 description 1
- ZDXCUOZNBYWYAI-UHFFFAOYSA-N 4-amino-2-phenylcyclohexa-1,5-diene-1,4-diol Chemical compound C1=CC(N)(O)CC(C=2C=CC=CC=2)=C1O ZDXCUOZNBYWYAI-UHFFFAOYSA-N 0.000 description 1
- DLTJSUIWKCLTFB-UHFFFAOYSA-N 5-phenylcyclohexa-2,4-diene-1,1,4-triol Chemical compound C1C(O)(O)C=CC(O)=C1C1=CC=CC=C1 DLTJSUIWKCLTFB-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000005243 carbonyl alkyl group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/56—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups
- C07C47/57—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/24—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
- C07C49/245—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/83—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/02—Quinones with monocyclic quinoid structure
- C07C50/06—Quinones with monocyclic quinoid structure with unsaturation outside the quinoid structure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
- C07C50/28—Quinones containing groups having oxygen atoms singly bound to carbon atoms with monocyclic quinoid structure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/38—Quinones containing —CHO or non—quinoid keto groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
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Description
149456
Den foreliggende opfindelse angår polyalkylenglycol stabiliseret mod mole-kylnedbrydning og viskositetstab ved hjælp af et hydroquinonderivat.
Det er kendt, at polyalkylenglycoler i almindelighed er forbindelser med :nskaber, der gør dem anvendelige på mange områder. De har en god smøreevne, t viskositetsindeks, lavt flydepunkt, gode diatermiske egenskaber og ubetydé-; korrosionsvirkning på metaller.
De anvendes derfor sædvanligvis som hydrauliske væsker, som smøremidler maskiner og som diatermiske eller varmegennemtrængelige væsker.
Uheldigvis har dé en ringe stabilitet over for oxidation, og allerede ved e temperaturer, ved ca. 35°C, oxideres de i atmosfærisk luft.
149456 2
Seres ringe stabilitet over for oxidation skyldes, at der let sker dannelse af hydroperoxider på grund af tilstedeværelse i molekylerne af C-H-bindinger nabostillet til oxygenatomer, hvilke bindinger er særligt reaktive over for radikaler, der frembringer oxidationskæder.
De dannede hydroperoxider er termisk instabile, og deres nedbrydning bevirker opbrydning af makromolekylet og dannelse af flygtige fragmenter med deraf følgende viskositetstab og vægttab for polyalkylenglycolen.
Ved moderate temperaturer indebærer stabiliseringen mod oxidation ingen problemer, da de fleste sædvanlige anti-oxidanter, såsom 2,6-di-tert.-butyl-p-cresol, hydroquinon eller phenyl-alpha-naphthylamin, giver tilstrækkeligt effektive resultater.
Inhibitionen bliver problematisk ved temperaturer højere end 150°C, når nævnte inhibitorer mod frie radikaler mister deres effektivitet. Således mister for eksempel den fra US patentskrift 3.278.473 som inhibitor kendte tert.-butyl-hydroquinon hurtigt sin virkning ved sådanne temperaturer. Det er antaget, at dette skyldes det forhold, at nævnte inhibitorer ved disse temperaturer gøres inaktive ved en direkte oxidation med oxygen.
Den væsentligste grund til, at de er ineffektive, er imidlertid instabiliteten af de i den første fase af oxidationen dannede hydroperoxider, der ved dekomponering frigør et stort antal radikaler, som hurtigt opbruger inhibitorerne.
Det har nu overraskende vist sig, at polyalkylenglycoler kan stabiliseres effektivt mod molekylnedbrydning og viskositetstab også ved høje temperaturer (>150°C) ved hjælp af forbindelser fra arylhydroquinon-klassen.
Opfindelsen angår derfor polyalkylenglycol stabiliseret mod molekylnedbrydning og viskositetstab ved hjælp af et hydroquinonderivat og er ejendommelig ved, at hydroquinonderivatet foreligger i en mængde på 0,001 til 10 vægtZ, fortrinsvis fra 0,1 til 2 vægt% og har den almene formel: i OH .
hvor R er hydrogen, en alkyl-, aryl-, kondenseret aryl-, arylalkyl-, hydroxy-, substitueret hydroxy-, amin-, substitueret amin-, carboxyl-, substitueret car- 149456 3 boxyl-, aldehyd-, carbonylalkyl-, carbonylaryl-, cyano- eller nitro-gruppe eller et halogen, og R kan have op til 10 carbonatomer.
Den i hvert enkelt tilfælde anvendte stabilisatormængde kan afhænge af strukturen af polyalkylenglycolen og det tilsigtede anvendelsesområde for denne.
Fremstillingen af de ifølge opfindelsen anvendte derivater af arylhydro-quinonderivater er beskrevet i litteraturen. Den kan for eksempel foregå ved fremgangsmåden beskrevet af D. E. Kvalnes, J. Am. Chem. Soc., 56, 2478 (1934).
Opfindelsen skal beskrives næmere gennem følgende eksempler, hvoraf eksemplerne 1-5 illustrerer fremstillingen åf forskellige af de til polyalkylenglycolen ifølge opfindelsen anvendte arylhydroquinoner.
Eksempel 1
Fremstilling af phenylhydroquinon.
18,3 ml Anilin blev diazoteret på sædvanlig måde i den mindst mulige mængde vand.
Opløsningen af det resulterende diazoniumsalt blev langsomt sat til en kraftigt omrørt suspension af 18 g p-benzoquinon i 500 ml vand, indeholdende et overskud af natriumbicarbonat og holdt ved 15°C.
Udvikling af nitrogen blev iagttaget, og phenylquinon blev udskilt fra blandingen. Udbyttet af det rå produkt, der blev isoleret ved filtrering og vasket med 1 liter vand, var 79%. Efter krystallisation fra. ligroin.fandtes et smeltepunkt på 112° til 113°C.
Phenylquinonen blev derefter reduceret til phenylhydroquinon ved anvendelse af et overskud af natriumbisulfit i en vandig alkoholisk opløsning. Efter ekstraktion med chloroform blev phenylhydroquinonen krystalliseret af methylenchlo-rid, smp. 96 - 98°C.
Eksempel 2
Fremstilling af phenylhydroquinon.
17 g o-Phenylphenol, opløst i en 10 %’s NaOH-opløsning, blev oxideret ved en temperatur på 15-20°C ved tilsætning under omrøring af en mættet vandig opløsning indeholdende 26 g kaliumpersulfat.
Den resulterende blanding blev henstillet natten over og derefter neutraliseret og filtreret.
Nævnte opløsning blev derefter behandlet med et overskud af HC1, opvarmet til kogning i 2 timer, afkølet og ekstraheret med ether. Afdampning af etheren gav en inddampningsrest bestående af den rå phenylhydroquinon i et udbytte på 32%.
Efter krystallisation af produktet af methylenchlorid var smp. 94-96°C.
4 U9456
Eksempel 3
Fremstilling af p-methylphenylhydroquinon.
Ved anvendelse af samme operationsbetingelser som i eksempel 1 og ud fra p-methylanilin og o-benzoquinon vandtes p-methylphenylquinon i et udbytte på 65%, smp. 135-137°G (krystallisationsopløsningsmiddel: ligroin), og ved at reducere det resulterende produkt vandtes p-methylphenylhydroquinon med smp. 116-117°C (krystallisationsopløsningsmiddel: methylenchlorid).
Eksempel 4
Fremstilling af p-methoxyphenylhydroquinon.
Ved anvendelse af de i eksempel 1 beskrevne operationsbetingelser og ud fra p-methoxyanilin og p-benzoquinon vandtes p-methoxyphenylquinon, udbytte 91%, smp. 119-120°C (krystallisationsopløsningsmiddel: vand/alkohol), og ved at reducere denne vandtes p-methoxyphenylhydroquinon med smp. 108-109°C (krystallisationsopløsningsmiddel : methylenchlorid).
Eksempel 5
Fremstilling af p-acetylphenylhydroquinon.
Ved at anvende samme operationsbetingelser, som beskrevet i eksempel 1, og ud fra p-acetyl-anilin og p-benzoquinon vandtes p-acetylphenylquinon, udbytte 88%, smp. 151-152°G (krystallisationsopløsningsmiddel: ligroin/chloroform), og ved reduktion deraf vandtes p-acetylphenylhydroquinon med smp. 190-191°C (krystallisationsopløsningsmiddel: methylenchlorid).
Eksempel 6
Den usædvanlige effektivitet af arylhydroquinoner til beskyttelse af poly-alkylenglycoler. mod oxidation blev påvist ved at sammenligne deres induktionsperioder med induktionsperioderne for de mest anvendte, anti-oxidanter ved oxygenabsorptionsprøver.
Prøverne blev gennemført med et apparat analogt med apparatet beskrevet af M.A.M. Bradney, A.D. Forbes (Chem.Ind. 15, 495, 1970): En konstant strøm af at- mosfærisk luft blev ledt hen over ·forsøgsprøven, der holdtes under kraftig omrøring med en lille magnetrotationsomrører i en dobbeltvægget celle, der var ter-mostateret ved forsøgstemperaturen ved hjælp af en oliecirkulation.
Absorptionen af oxygen fremgik af en analysator for C^-procent, hvilken analysators elektriske signal blev forarbejdet af et elektronisk kompleks, der automatisk angav absorptionshastigheden og den totale absorption af oxygen.
Den ved hjælp af dette apparat målte induktionsperiode blev fastsat som den tid, efter hvilken der indtraf en pludselig stigning i oxidationshastigheden, der skyldes afslutning af den hæmmende virkning.
149456 5
Resultaterne af forsøg, der blev gennemført ved 197 ί 0,2°C, på prøver på 3 g baseret på polypropylenglycol med en molekylvagt på 1400, omrørt ved 1000 3 r.p.m. og ved anvendelse af en strøm af atmosfærisk luft på 50 cm /min., er anført i tabel I.
Tabel I
Oxidationsforsøg i strøn af atmosfærisk luft (50 cm-3/min.) ved 197°C Basisolie: polypropylenglycol (molvægt = 1400)
Tilsætning Induktionstid (min.) __________________________________________________0,5%_____1%____2 % (vægt/vægt)
Sammenligning; 2.6- di-tert.-butyl-4-methylphenol 1 2 22 phenyl-alpha-naphthylamin 1 3 120 3.6- dioctylphenothiazin 10 70 210 hydroquinon 45 90 140 tert.-butylhydroquinon 32 53 87 pyrocatechol . 1 3 40
Ifølge opfindelsen: .
phenylhydroquinon 60 175 410 p-methylphenylhydroquinon 110 235 465 p-methoxyphenylhydroquinon 58 165 395 p-acetylphenylhydroquinon 75 315 >500
Disse forsøgsresultater viser, at de til stabiliseret polyalkylenglycol ifølge opfindelsen som stabilisatorer anvendte hydroquinonderivater stabiliserer mod molekylnedbrydning' ved oxidation over en væsentlig længere periode end de til sammenligning anvendte kendte stabilisatorer.
Eksempel 7
Til påvisning af effektiviteten af nogle af de omhandlede arylhydroquino-nér til beskyttelse af polyalkylenglycoler mod nedbrydning skal anføres bestemmelser af viskositets- og vægtvariationer deraf efter oxidationsforsøg i nærværelse af en kobberstrimmel.
Forsøgene bestod i at bringe en strøm af atmosfærisk luft med ensartet hastighed til at boble gennem forsøgsprøven. Denne prøve var indeholdt.i en glascylinder, hvori en kobberstrimmel var neddykket, og som var termostateret ved forsøgstemperaturen i en aluminiumsvarmeblok.
149456 6
Efter endt forsøg blev de procentuelle variationer for polyalkylenglycol-viskositet og -vægt og den procentuelle variation i strimmelvægt målt.
Resultaterne fra oxidationsforsøg gennemført ved temperaturer på 160 ΐ 0,2°C
på prøver baseret på polyethylen-propylenglyco1 med molekylvægt = 1500, ved an- 3 vendelse af en strøm af atmosfærisk luft på 50 cm /minut i 96 timer, er anført i tabel II.
Tabel II
3
Oxidationsforsøg med bobling af atmosfærisk luft (50 cm /min.) i nærværelse af kobberstrimmel véd en temperatur = 160°C. Basisolie: polyethylen-propylenglycol (molvægt -= 1500).
Tilsætning vægt-% Procentuel Procentuel Procentuel viskositets* vægtvariation vægtvariation variation for poly- for strimmel ved 37,8°C glycol - 49,50 - 7,43 - 0,14 3,6-dioctylphenothiazin 2 - 21,22 - 3,57 - 0,03 ρ,ρ'-dioctyldiphenylamin 2 - 41,87 - 4,42 - 0,03 hydroquinon 2 -6,99 -1,14 -0,09 phenyl-alpha-naphthylamin 2 - 9,80 - 1,71 - 0,25 phenylhydroquinon 2 +3,53 - 0,25 - 0,04 p-acetylphenylhydroquinon 2 +3,11 - 0,19 - 0,06 p-methoxyphenylhydroquinon 2 +2,14 - 0,14 - 0,07 p-methylphenylhydroquinon 2 + 2,82 - 0,11 - 0,09 m-nitrophenylhydroquinon 1 - 3,80 - 1,01 - 0,03 m-chlorophenylhydroquinon 1 - 2,74 - 1,25 - 0,02 p-phenyIphenyIhydrqquinon 1 -5,37 -1,41 -0,11 p-carboxyphenylhydroquinon 1 - 2,34 - 0,87 - 0,12 β-naphthylhydroquinon 1 - 4,53 - 1,07 - 0,04 p-hydroxyphenylhydroquinon 2 +3,14 - 0,17 - 0,07 p-aminophenylhydroquinon 2 + 3,24 - 0,18 - 0,08
Disse forsøgsresultater viser, at de til stabiliseret polyalkylenglycol ifølge opfindelsen som stabilisatorer anvendte hydroquinonderivater stabiliserer væsentligt bedre mod viskositetstab under oxidative betingelser end de til sammenligning anvendte kendte stabilisatorer, ligesom også den procentuelle vægtvariation ligger på et meget lavt niveau.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24790/74A IT1015667B (it) | 1974-07-04 | 1974-07-04 | Poliglicoli stabilizzati per alte temperature |
| IT2479074 | 1974-07-04 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK301575A DK301575A (da) | 1976-01-05 |
| DK149456B true DK149456B (da) | 1986-06-16 |
| DK149456C DK149456C (da) | 1986-11-10 |
Family
ID=11214748
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK301575A DK149456C (da) | 1974-07-04 | 1975-07-03 | Polyakylenglycol stabiliseret mod molekylnedbrydning og viskositetstab ved hjaelp af et hydroquinonderivat |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4016211A (da) |
| JP (1) | JPS5634030B2 (da) |
| AT (1) | AT350271B (da) |
| BE (1) | BE830962A (da) |
| CH (1) | CH606220A5 (da) |
| DD (1) | DD118666A5 (da) |
| DE (1) | DE2530004C3 (da) |
| DK (1) | DK149456C (da) |
| FR (1) | FR2277142A1 (da) |
| GB (1) | GB1496169A (da) |
| IE (1) | IE41626B1 (da) |
| IT (1) | IT1015667B (da) |
| LU (1) | LU72891A1 (da) |
| NL (1) | NL157039B (da) |
| NO (1) | NO143462C (da) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847429A (en) * | 1987-08-03 | 1989-07-11 | Eastman Kodak Company | Synthesis of phenylhydroquinones |
| JPH01173417U (da) * | 1988-05-24 | 1989-12-08 | ||
| US4960957A (en) * | 1989-05-30 | 1990-10-02 | E. I. Du Pont De Nemours And Company | Preparation of phenylhydroquinone |
| FR2716457B1 (fr) * | 1994-02-23 | 1996-05-24 | Saint Gobain Vitrage Int | Matériau électrolyte conducteur protonique. |
| DE19843730A1 (de) * | 1998-09-24 | 2000-03-30 | Sueddeutsche Kalkstickstoff | Stabilisierte, wasserlösliche Polymerpulver auf Basis von Polyoxyalkylenglykol-Carboxylaten und Verfahren zu deren Herstellung |
| US9708547B2 (en) * | 2007-10-15 | 2017-07-18 | Baker Hughes Incorporated | Water-based formulation of H2S/mercaptan scavenger for fluids in oilfield and refinery applications |
| CN101463128B (zh) * | 2008-12-30 | 2011-12-07 | 吉林大学 | 含氨基苯侧基的聚芳醚类聚合物及其合成方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2641614A (en) * | 1953-06-09 | Condensation products of styrene | ||
| US2942033A (en) * | 1960-06-21 | Stabilization of polyoxyalkylene | ||
| US2687378A (en) * | 1951-12-11 | 1954-08-24 | California Research Corp | Lubricating oil composition |
| US2736709A (en) * | 1954-08-17 | 1956-02-28 | Gen Aniline & Film Corp | Hydraulic fluids |
-
1974
- 1974-07-04 IT IT24790/74A patent/IT1015667B/it active
-
1975
- 1975-06-19 GB GB26198/75A patent/GB1496169A/en not_active Expired
- 1975-06-24 IE IE1398/75A patent/IE41626B1/en unknown
- 1975-06-25 CH CH826575A patent/CH606220A5/xx not_active IP Right Cessation
- 1975-06-26 NO NO752308A patent/NO143462C/no unknown
- 1975-06-30 FR FR7520484A patent/FR2277142A1/fr active Granted
- 1975-07-02 DD DD187040A patent/DD118666A5/xx unknown
- 1975-07-03 BE BE157945A patent/BE830962A/xx not_active IP Right Cessation
- 1975-07-03 NL NL7507960.A patent/NL157039B/xx not_active IP Right Cessation
- 1975-07-03 US US05/592,728 patent/US4016211A/en not_active Expired - Lifetime
- 1975-07-03 AT AT512875A patent/AT350271B/de active
- 1975-07-03 LU LU72891A patent/LU72891A1/xx unknown
- 1975-07-03 DK DK301575A patent/DK149456C/da not_active IP Right Cessation
- 1975-07-04 DE DE2530004A patent/DE2530004C3/de not_active Expired
- 1975-07-04 JP JP8198775A patent/JPS5634030B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT1015667B (it) | 1977-05-20 |
| CH606220A5 (da) | 1978-10-31 |
| JPS5634030B2 (da) | 1981-08-07 |
| DD118666A5 (da) | 1976-03-12 |
| US4016211A (en) | 1977-04-05 |
| DE2530004C3 (de) | 1978-08-17 |
| NO143462C (no) | 1981-02-18 |
| JPS5130853A (da) | 1976-03-16 |
| NL157039B (nl) | 1978-06-15 |
| NO752308L (da) | 1976-01-06 |
| NL7507960A (nl) | 1976-01-06 |
| AT350271B (de) | 1979-05-25 |
| DE2530004A1 (de) | 1976-01-22 |
| ATA512875A (de) | 1978-10-15 |
| LU72891A1 (da) | 1975-12-09 |
| DK149456C (da) | 1986-11-10 |
| IE41626B1 (en) | 1980-02-13 |
| DE2530004B2 (de) | 1977-12-08 |
| NO143462B (no) | 1980-11-10 |
| GB1496169A (en) | 1977-12-30 |
| FR2277142B1 (da) | 1979-06-15 |
| FR2277142A1 (fr) | 1976-01-30 |
| BE830962A (fr) | 1975-11-03 |
| DK301575A (da) | 1976-01-05 |
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