DE19822235A1 - Novel esters of unsaturated etheralcohols with functionalized fatty acids, useful as stabilisers, lubricants and/or plasticizers for plastics - Google Patents
Novel esters of unsaturated etheralcohols with functionalized fatty acids, useful as stabilisers, lubricants and/or plasticizers for plasticsInfo
- Publication number
- DE19822235A1 DE19822235A1 DE1998122235 DE19822235A DE19822235A1 DE 19822235 A1 DE19822235 A1 DE 19822235A1 DE 1998122235 DE1998122235 DE 1998122235 DE 19822235 A DE19822235 A DE 19822235A DE 19822235 A1 DE19822235 A1 DE 19822235A1
- Authority
- DE
- Germany
- Prior art keywords
- fatty acids
- group
- unsaturated
- esters
- ester
- 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.)
- Granted
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 20
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 20
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 18
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 18
- 239000000194 fatty acid Substances 0.000 title claims abstract description 18
- 239000000314 lubricant Substances 0.000 title claims description 4
- 239000003381 stabilizer Substances 0.000 title claims description 4
- 239000004033 plastic Substances 0.000 title description 2
- 229920003023 plastic Polymers 0.000 title description 2
- 239000004014 plasticizer Substances 0.000 title 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 8
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- -1 unsaturated ether alcohols Chemical class 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000000466 oxiranyl group Chemical group 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000003003 phosphines Chemical class 0.000 claims description 3
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 3
- 229960003656 ricinoleic acid Drugs 0.000 claims description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001414 amino alcohols Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000008031 plastic plasticizer Substances 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 3
- 238000007363 ring formation reaction Methods 0.000 claims 2
- 101100495769 Caenorhabditis elegans che-1 gene Proteins 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- 238000005755 formation reaction Methods 0.000 claims 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 claims 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 9
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical class C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 235000019486 Sunflower oil Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000002600 sunflower oil Substances 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 241000208818 Helianthus Species 0.000 description 2
- 235000003222 Helianthus annuus Nutrition 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- YAXKTBLXMTYWDQ-UHFFFAOYSA-N 1,2,3-butanetriol Chemical compound CC(O)C(O)CO YAXKTBLXMTYWDQ-UHFFFAOYSA-N 0.000 description 1
- SXNBVULTHKFMNO-UHFFFAOYSA-N 2,2-dihydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)(O)C(O)=O SXNBVULTHKFMNO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- 235000000540 Brassica rapa subsp rapa Nutrition 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 241000158147 Sator Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- DTOSIQBPPRVQHS-UHFFFAOYSA-N α-Linolenic acid Chemical compound CCC=CCC=CCC=CCCCCCCCC(O)=O DTOSIQBPPRVQHS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
-
- 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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Gegenstand der Erfindung sind Ester ungesättigter Etheralkohole mit funktionalisierten Fettsäuren, ein Verfahren zu deren Her stellung und deren Verwendung.The invention relates to esters of unsaturated ether alcohols with functionalized fatty acids, a process for their preparation position and its use.
Die erfindungsgemäßen Ester besitzen die folgende allgemeine
Formel
The esters according to the invention have the following general formula
in der
in the
- - R eine verzweigte oder unverzweigte Kohlenwasserstoffgruppe ist, die sich von einem verzweigten oder unverzweigten, mehrwertigen Alkohol ableitet, - R is a branched or unbranched hydrocarbon group is that of a branched or unbranched, derives polyhydric alcohol,
- - R1 eine einfach oder mehrfach epoxidierte und/oder hydroxy lierte Kohlenwasserstoffgruppe mit 16 bis 24 Kohlenstoff atomen ist,R 1 is a single or multiple epoxidized and / or hydroxylated hydrocarbon group with 16 to 24 carbon atoms,
- - R2 Wasserstoff oder eine Alkylgruppe ist,R 2 is hydrogen or an alkyl group,
- - R3 eine CH2-Gruppe ist,R 3 is a CH 2 group,
- - m und n jeweils ganze Zahlen darstellen, deren Summe minde stens 2 beträgt, und- m and n each represent integers, the sum of which is at least is at least 2, and
- - x Null oder eine ganze Zahl von 1 bis 7 ist.- x is zero or an integer from 1 to 7.
Die erfindungsgemäß bevorzugten epoxidierten Allylether-Ester (x = 0) können nach allgemein bekannten Verfahren hergestellt werden durch Veresterung geeigneter Allylether mehrwertiger Alkohole mit noch einer oder mehreren freien Hydroxylgruppen mit geeigneten ungesättigten Fettsäuren oder Mischungen aus ungesät tigten Fettsäuren. Die derart erhaltenen ungesättigten Ether- Ester werden anschließend nach ebenfalls allgemein bekannten Verfahren epoxidiert, wobei lediglich die Doppelbindungen der ungesättigten Fettsäuren, nicht aber die Doppelbindungen der Allyl-Gruppen zu Oxiran-Gruppen umgewandelt werden. Die erfin dungsgemäßen epoxidierten Ether-Ester besitzen also neben Oxi ran-Gruppen auch noch ungesättigte Gruppen in dem Alkoholrest. Wenn die Allylether der mehrwertigen Alkohole mehr als eine freie Hydroxylgruppe aufweisen, reicht es, wenn nur eine Hydro xylgruppe verestert wird. Die weiteren freien Hydroxylgruppen können ebenfalls ganz oder teilweise verestert werden. In ent sprechender Weise reicht es bei Verwendung von mehrfach ungesät tigten Fettsäuren, wenn lediglich eine Doppelbindung epoxidiert wird. Die weiteren vorhandenen Doppelbindungen können jedoch ebenfalls ganz oder teilweise epoxidiert werden. The epoxidized allyl ether esters preferred according to the invention (x = 0) can be produced by generally known methods become more polyvalent by esterification of suitable allyl ethers Alcohols with one or more free hydroxyl groups suitable unsaturated fatty acids or mixtures of unsaturated saturated fatty acids. The unsaturated ether Esters are then also generally known Process epoxidized, whereby only the double bonds of unsaturated fatty acids, but not the double bonds of Allyl groups are converted to oxirane groups. The invent epoxidized ether esters according to the invention thus have in addition to oxi ran groups also unsaturated groups in the alcohol residue. If the allyl ethers of the polyhydric alcohols have more than one have free hydroxyl group, it is sufficient if only one hydro xyl group is esterified. The other free hydroxyl groups can also be esterified in whole or in part. In ent speaking it is sufficient when using multiple unseeded fatty acids if only one double bond epoxidizes becomes. However, the other double bonds present can can also be completely or partially epoxidized.
Die erfindungsgemäß bevorzugten hydroxylierten Allylether-Ester (x = 0) können nach allgemein bekannten Verfahren hergestellt werden durch Veresterung geeigneter Allylether mehrwertiger Alkohole mit noch einer oder mehreren freien Hydroxylgruppen mit geeigneten hydroxylierten Fettsäuren (Hydroxyfettsäuren). Die Herstellung geeigneter hydroxylierter Fettsäuren ist beispiels weise in EP 0 554 590 B1 und DE 43 32 292 A1 ausführlich be schrieben. Die erfindungsgemäßen hydroxylierten Ether-Ester besitzen also neben Hydroxylgruppen in der Fettsäurekette auch noch ungesättigte Gruppen in dem Alkoholrest. Natürlich erhält man erfindungsgemäße hydroxylierte Allylether-Ester auch, wenn man die oben beschriebenen epoxidierten Allylether-Ester unter Ringöffnung der Oxiran-Gruppe mit Wasser in Gegenwart eines geeigneten Katalysators umsetzt (siehe DE 41 25 031 C1). Außer dem gilt auch hier, daß bei Verwendung von Allylethern mehrwer tiger Alkohole mit noch mehreren freien Hydroxylgruppen nur eine Hydroxylgruppe verestert werden muß, während die anderen freien Hydroxylgruppen nicht, teilweise oder vollständig verestert werden können.The preferred hydroxylated allyl ether esters according to the invention (x = 0) can be produced by generally known methods become more polyvalent by esterification of suitable allyl ethers Alcohols with one or more free hydroxyl groups suitable hydroxylated fatty acids (hydroxy fatty acids). The Production of suitable hydroxylated fatty acids is an example as described in EP 0 554 590 B1 and DE 43 32 292 A1 wrote. The hydroxylated ether esters according to the invention have in addition to hydroxyl groups in the fatty acid chain still unsaturated groups in the alcohol residue. Obviously receives one also hydroxylated allyl ether esters according to the invention if the epoxidized allyl ether esters described above Ring opening of the oxirane group with water in the presence of a suitable catalyst (see DE 41 25 031 C1). Except this also applies here that more is used when using allyl ethers tiger alcohols with more free hydroxyl groups only one Hydroxyl group must be esterified while the others are free Hydroxyl groups not, partially or completely esterified can be.
Anstelle von Allylethern können auch die entsprechenden Homologe mit endständigen Doppelbindungen (x = 1 bis 7) eingesetzt wer den.The corresponding homologs can also be used instead of allyl ethers with terminal double bonds (x = 1 to 7) who used the.
Geeignete mehrwertige Alkohole, auf die R zurückgeht, leiten sich beispielsweise von Glykol, Glycerin, Trimethylolpropan, 1,2,3-Butantriol, Pentaerythrit und Sorbit ab. Vorzugsweise weist R 2 bis 6 Kohlenstoffatome auf.Appropriate polyhydric alcohols, to which R is based, conduct for example from glycol, glycerin, trimethylolpropane, 1,2,3-butanetriol, pentaerythritol and sorbitol. Preferably R has 2 to 6 carbon atoms.
Als Fettsäuren eignen sich ungesättigte Carbonsäuren wie Öl-, Linol-, Linolen- und Ricinolsäure sowie deren natürlich vorkom mende Gemische aus pflanzlichen Ölen wie z. B. Rüböl, Sonnenblu menöl, Sojaöl, Leinöl, Ricinolsäure und andere überwiegend unge sättigte pflanzliche und tierische Öle und Fette. Unsaturated carboxylic acids such as oleic, Linoleic, linolenic and ricinoleic acid and their naturally occurring Mixtures of vegetable oils such as. B. turnip oil, sunflower menöl, soybean oil, linseed oil, ricinoleic acid and others mostly unused saturated vegetable and animal oils and fats.
Die Summe von m und n beträgt mindestens 2 und vorzugsweise mindestens 3.The sum of m and n is at least 2 and preferably at least 3.
Wenn R2 eine Alkylgruppe ist, weist sie vorzugsweise 1 bis 3 Kohlenstoffatome auf.When R 2 is an alkyl group, it preferably has 1 to 3 carbon atoms.
Die funktionalisierten Fettsäurereste in den erfindungsgemäßen Ether-Estern können gewünschtenfalls Seitengruppen aufweisen. Bevorzugt handelt es sich hierbei um Alkoxygruppen, die entweder durch Verwendung von bereits alkoxylierten hydroxylierten Fett säuren oder durch Ringöffnung der in den epoxidierten Ether- Estern vorhandenen Oxiran-Gruppen durch Umsetzung mit einer aktiven Wasserstoff enthaltenden Verbindung, insbesondere einem Alkohol in die erfindungsgemäßen Ether-Ester eingebracht werden. Zu den geeigneten aktiven Wasserstoff enthaltenden Verbindungen sei auf EP 0 554 590 B1 verwiesen. Es handelt sich hierbei im wesentlichen um Alkohole, Phenole, Aminoalkohole, Amine, Mercap tane, organische Phosphorwasserstoffverbindungen (Phosphine), Carbonsäuren und Halogenwasserstoffe. Als Alkohole sind auch die erfindungsgemäß als Ausgangsverbindungen verwendeten ungesättig ten Ether mehrwertiger Alkohole mit noch einer oder mehreren freien Hydroxylgruppen geeignet (siehe Beispiel 3).The functionalized fatty acid residues in the invention If desired, ether esters can have side groups. These are preferably alkoxy groups, which are either by using already alkoxylated hydroxylated fat acids or by opening the ring in the epoxidized ether Ester present oxirane groups by reaction with a active hydrogen-containing compound, in particular a Alcohol can be introduced into the ether esters according to the invention. To the suitable active hydrogen containing compounds please refer to EP 0 554 590 B1. It is in the essential to alcohols, phenols, amino alcohols, amines, mercap tane, organic phosphine compounds (phosphines), Carboxylic acids and hydrogen halides. They are also alcohols unsaturated used according to the invention as starting compounds th ether of polyhydric alcohols with one or more suitable free hydroxyl groups (see Example 3).
Die erfindungsgemäßen Ester ungesättigter Etheralkohole besitzen ein beachtliches Potential als hervorragende organische Stabili satoren und Gleitmittel für Kunststoffe, insbesondere PVC, und stellen somit eine Alternative zu herkömmlichen Stabilisatoren und Gleitmitteln zum Beispiel auf Basis von Schwermetallseifen, insbesondere Bleiverbindungen, dar. Darüber hinaus eignen sie sich auch als Weichmacher für Kunststoffe.The esters of unsaturated ether alcohols according to the invention have considerable potential as excellent organic stabilizers sators and lubricants for plastics, in particular PVC, and represent an alternative to conventional stabilizers and lubricants, for example based on heavy metal soaps, especially lead compounds. They are also suitable also as a plasticizer for plastics.
Sonnenblumenölfettsäure (688 g) und Trimethylolpropan-Diallyl
ether (572 g) wurden bei 230°C unter azeotroper Abscheidung des
Reaktionswassers mittels Xylol über einen Zeitraum von 6 Stunden
verestert. Nach beendeter Veresterung wurden das Xylol und ge
ringe Anteile von nicht-umgesetztem TMP-Diallylether unter Was
serstrahl-Vakuum abdestilliert. Der derart hergestellte ungesät
tigte Allyl-Ester wurde nach bekanntem Verfahren epoxidiert. Die
epoxidierte Verbindung hatte folgende Kennzahlen:
Säurezahl: 11
Jodzahl: 67
Oxirangehalt, %: 4,2
Viskosität bei 25°C, mPa.s: 105
Farbzahl (Gardner): 1
Hydroxylzahl: 38Sunflower oil fatty acid (688 g) and trimethylolpropane diallyl ether (572 g) were esterified at 230 ° C. with azeotropic separation of the water of reaction with xylene over a period of 6 hours. After the esterification had ended, the xylene and small amounts of unreacted TMP diallyl ether were distilled off under water jet vacuum. The unsaturated allyl ester thus prepared was epoxidized by a known method. The epoxidized compound had the following key figures:
Acid number: 11
Iodine number: 67
Oxirane content,%: 4.2
Viscosity at 25 ° C, mPa.s: 105
Color number (Gardner): 1
Hydroxyl number: 38
Sonnenblumenölfettsäure (1500 g) und Pentaerythrit-Triallylether
(1430 g) wurden bei 230°C unter azeotroper Abscheidung des
Reaktionswassers mittels Xylol über einen Zeitraum von 3 Stunden
verestert. Nach beendeter Veresterung wurden das Xylol und ge
ringe Anteile von nicht-umgesetztem Pentaerythrit-Triallylether
unter Wasserstrahl-Vakuum abdestilliert. Der derart hergestellte
ungesättigte Allyl-Ester wurde nach bekanntem Verfahren epoxi
diert. Die epoxidierte Verbindung hatte folgende Kennzahlen:
Säurezahl: 12
Jodzahl: 99
Oxirangehalt, %: 5,1
Viskosität bei 25°C, mPa.s: 115
Farbzahl (Gardner): 1
Hydroxylzahl: 42Sunflower oil fatty acid (1500 g) and pentaerythritol triallyl ether (1430 g) were esterified at 230 ° C. with azeotropic separation of the water of reaction with xylene over a period of 3 hours. After the esterification had ended, the xylene and small amounts of unreacted pentaerythritol triallyl ether were distilled off under a water jet vacuum. The unsaturated allyl ester prepared in this way was epoxidized by a known method. The epoxidized compound had the following key figures:
Acid number: 12
Iodine number: 99
Oxirane content,%: 5.1
Viscosity at 25 ° C, mPa.s: 115
Color number (Gardner): 1
Hydroxyl number: 42
Weitere Umsetzungen an den Epoxid-Gruppen der epoxidierten
Allylether-Ester gemäß Beispiel 2 mit dem Ziel einer Ringöffnung
(Alkoxylierung) mit z. B. monofunktionellen Allylverbindungen wie
Allylalkohol und/oder polyfunktionellen Allylverbindungen ent
sprechend den vorstehend genannten Allylether-Alkoholen sind
durch EP 0 554 590 B1 abgedeckt. So führte z. B. die Alkoxylie
rung des in Beispiel 2 genannten epoxidierten Allylether-Esters
mit Pentaerythrit-Triallylether zu einem Produkt mit folgenden
Kennzahlen:
Säurezahl: 1,6
Jodzahl: 134
Hydroxylzahl: 139
Viskosität bei 25°C, mPa.s: 2600
Farbzahl (Gardner): 6Further reactions on the epoxy groups of the epoxidized allyl ether esters according to Example 2 with the aim of ring opening (alkoxylation) with z. B. monofunctional allyl compounds such as allyl alcohol and / or polyfunctional allyl compounds accordingly the above-mentioned allyl ether alcohols are covered by EP 0 554 590 B1. So z. B. Alkoxylie tion of the epoxidized allyl ether mentioned in Example 2 with pentaerythritol triallyl ether to a product with the following key figures:
Acid number: 1.6
Iodine number: 134
Hydroxyl number: 139
Viscosity at 25 ° C, mPa.s: 2600
Color number (Gardner): 6
Dihydroxystearinsäure (700 g) und Pentaerythrit-Triallylether
(525 g) wurden bei 230°C unter azeotroper Abscheidung des Reak
tionswassers mittels Xylol über einen Zeitraum von 3 Stunden
verestert. Nach beendeter Veresterung wurden das Xylol und ge
ringe Anteile von nicht-umgesetztem Pentaerythrit-Triallylether
unter Wasserstrahl-Vakuum abdestilliert. Der anfallende hydroxy
lierte Ether-Ester hatte folgende Kennzahlen:
Säurezahl: 0,5
Jodzahl: 106
Viskosität bei 25°C, mPa.s: 560
Farbzahl (Gardner): 6
Hydroxylzahl: 187Dihydroxystearic acid (700 g) and pentaerythritol triallyl ether (525 g) were esterified at 230 ° C. with azeotropic separation of the reaction water with xylene over a period of 3 hours. After the esterification had ended, the xylene and small amounts of unreacted pentaerythritol triallyl ether were distilled off under a water jet vacuum. The resulting hydroxylated ether ester had the following key figures:
Acid number: 0.5
Iodine number: 106
Viscosity at 25 ° C, mPa.s: 560
Color number (Gardner): 6
Hydroxyl number: 187
Claims (10)
in der
- - R eine verzweigte oder unverzweigte Kohlenwasserstoff gruppe ist, die sich von einem verzweigten oder unver zweigten mehrwertigen Alkohol ableitet,
- - R1 eine einfach oder mehrfach epoxidierte und/oder hydroxylierte Kohlenwasserstoffgruppe mit 16 bis 24 Kohlenstoffatomen ist,
- - R2 Wasserstoff oder eine Alkylgruppe ist,
- - R3 eine CH2-Gruppe ist,
- - m und n jeweils ganze Zahlen darstellen, deren Summe mindestens 2 beträgt, und
- - x Null oder eine ganze Zahl von 1 bis 7 ist.
in the
- R is a branched or unbranched hydrocarbon group which is derived from a branched or unbranched polyhydric alcohol,
- R 1 is a single or multiple epoxidized and / or hydroxylated hydrocarbon group with 16 to 24 carbon atoms,
- R 2 is hydrogen or an alkyl group,
- R 3 is a CH 2 group,
- - m and n each represent integers, the sum of which is at least 2, and
- - x is zero or an integer from 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1998122235 DE19822235C2 (en) | 1998-05-07 | 1998-05-07 | Esters of unsaturated ether alcohols with functionalized fatty acids, processes for their production and their use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1998122235 DE19822235C2 (en) | 1998-05-07 | 1998-05-07 | Esters of unsaturated ether alcohols with functionalized fatty acids, processes for their production and their use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE19822235A1 true DE19822235A1 (en) | 1999-11-11 |
| DE19822235C2 DE19822235C2 (en) | 2001-03-08 |
Family
ID=7868152
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1998122235 Expired - Fee Related DE19822235C2 (en) | 1998-05-07 | 1998-05-07 | Esters of unsaturated ether alcohols with functionalized fatty acids, processes for their production and their use |
Country Status (1)
| Country | Link |
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| DE (1) | DE19822235C2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008028176A1 (en) * | 2006-09-01 | 2008-03-06 | The Curators Of The University Of Missouri | Soybean based epoxy resin and methods of making and use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4125031C1 (en) * | 1991-07-29 | 1993-02-25 | Harburger Fettchemie Brinckman & Mergell Gmbh, 2100 Hamburg, De | Prepn. of hydroxylated fatty acid, used to form polymer - comprises hydrolysing epoxidised fatty acid with oxirane rings in presence of activated catalyst e.g. alumina |
| EP0554590A2 (en) * | 1992-02-04 | 1993-08-11 | HARBURGER FETTCHEMIE BRINCKMAN & MERGELL GmbH | Process for the preparation of hydroxylated fatty acids |
| DE4332292A1 (en) * | 1993-09-20 | 1995-03-23 | Brinckmann Harburger Fett | Process for the direct hydroxylation of unsaturated carboxylic acids |
-
1998
- 1998-05-07 DE DE1998122235 patent/DE19822235C2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4125031C1 (en) * | 1991-07-29 | 1993-02-25 | Harburger Fettchemie Brinckman & Mergell Gmbh, 2100 Hamburg, De | Prepn. of hydroxylated fatty acid, used to form polymer - comprises hydrolysing epoxidised fatty acid with oxirane rings in presence of activated catalyst e.g. alumina |
| EP0554590A2 (en) * | 1992-02-04 | 1993-08-11 | HARBURGER FETTCHEMIE BRINCKMAN & MERGELL GmbH | Process for the preparation of hydroxylated fatty acids |
| DE4332292A1 (en) * | 1993-09-20 | 1995-03-23 | Brinckmann Harburger Fett | Process for the direct hydroxylation of unsaturated carboxylic acids |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008028176A1 (en) * | 2006-09-01 | 2008-03-06 | The Curators Of The University Of Missouri | Soybean based epoxy resin and methods of making and use |
| US8481622B2 (en) | 2006-09-01 | 2013-07-09 | The Curators Of The University Of Missouri | Soybean based epoxy resin and methods of making and use |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19822235C2 (en) | 2001-03-08 |
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