CA2053876A1 - Process for making 2-alkyl-or alkenyl-2-oxazolines from fatty acid glycerides - Google Patents
Process for making 2-alkyl-or alkenyl-2-oxazolines from fatty acid glyceridesInfo
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- CA2053876A1 CA2053876A1 CA 2053876 CA2053876A CA2053876A1 CA 2053876 A1 CA2053876 A1 CA 2053876A1 CA 2053876 CA2053876 CA 2053876 CA 2053876 A CA2053876 A CA 2053876A CA 2053876 A1 CA2053876 A1 CA 2053876A1
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- carbon atoms
- fatty acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D263/12—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals containing only hydrogen and carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT
A process for making 2-alkyl- or alkenyl-2-oxazolines, in which the alkyl or alkenyl group is a hydroxy-substituted hydrocarbon residue with at least 7 carbon atoms, produces the compounds of the title in large quantities if fatty acid glycerides with at least 8 carbon atoms are caused to react with 2-amino ethanol in the presence of titanium or zirconium compounds of the M(OR2)4 type (M = Ti or Zr).
A process for making 2-alkyl- or alkenyl-2-oxazolines, in which the alkyl or alkenyl group is a hydroxy-substituted hydrocarbon residue with at least 7 carbon atoms, produces the compounds of the title in large quantities if fatty acid glycerides with at least 8 carbon atoms are caused to react with 2-amino ethanol in the presence of titanium or zirconium compounds of the M(OR2)4 type (M = Ti or Zr).
Description
~i3~
WO 90/13545 1 PC~/EP90/00629 A process for the production of 2-alkyl or alkenyl-2-oxazolines from fatty acid glycerides This invention relates to a process for the production of 2-alkyl or alkenyl 2-oxazolines corresponding to general formula I
1'`3 '---I
R1~ ~ 0 J (I) in which Rl is an optionally hydroxy-substituted hydrocarbon radical containing at least 7 and, more particularly, 7 to 21 carbon atoms in the hydrocarbon chain, by condensation of fatty acid ethanolamides or fatty acid glycerides and 2-aminoethanol as precursors thereof in the liquid phase in the presence of catalysts.
WO 90/13545 1 PC~/EP90/00629 A process for the production of 2-alkyl or alkenyl-2-oxazolines from fatty acid glycerides This invention relates to a process for the production of 2-alkyl or alkenyl 2-oxazolines corresponding to general formula I
1'`3 '---I
R1~ ~ 0 J (I) in which Rl is an optionally hydroxy-substituted hydrocarbon radical containing at least 7 and, more particularly, 7 to 21 carbon atoms in the hydrocarbon chain, by condensation of fatty acid ethanolamides or fatty acid glycerides and 2-aminoethanol as precursors thereof in the liquid phase in the presence of catalysts.
2-Alkyl-substituted 2-oxazolines are valuable products which are used inter alia as solvents or plasticizers and, in particular, as polymerization components. Numerous processes have been described for the preparation of compounds of this class.
The most simple method is based on the cyclodehydra-tion of N-2-hydroxyethyl carboxylic acid amides (Chem. Rev.
44, 447 et ~g (1949), Chem. Rev. 71, 485 et ~g (1971)).
However, cyclization of the unsubstituted N-2-hydroxyethyl carboxylic acid amides requires very drastic conditions or the presence of special cataly~ts. Whereas gas-phase reac-tions in the presence of dehydrating metal oxides, such as Al203, SiOJAl2O3, Al2O3/TiO2, Tio2 or MgO, have proved to be s~itable for the preparation of readily volatile, short-c:hain 2-alkyl-2-oxazolines, the more volatile, relatively ; 30 long-chain 2-alkyl-2-oxazolines are better prepared in the liguid phase, Compounds of manganese, cobalt, molybdenum, X~5~37~
W0 90/13545 2 PC~/EP90/00629 tungsten, iron, cadmium, zinc and tin and also compounds of the rare earth metals have been described as catalysts for the liquid-phase reaction (cf. US-PS 3,562,263, BE-PS 666 829, C.A. 87, 135353, C.A. 87, 135352, US-PS 3,681,329, US-PS 3,681,333, EP-OS 0 033 752, US-PS 4,543,414, US~PS
4,354,029, US-PS 4,443,611, EP-OS 0 105 944 and EP-05 0 164 219)~ However, the catalysts described in the publications cited above do not lead to good yields in the production of relatively long-chain 2-fatty alkyl-2-oxazolines.
It has now been found that special titanium and zirconium compounds are eminently suitable as catalysts for a process of the type mentioned at the beginning, enabling yields of up to about 85~ of the theoretical, based on the starting compound, to be obtained.
Accordingly, the present invention relates to a process of the type mentioned at the beginning in which glycerides, more particularly triglycerides, of optionally hydroxy-substituted fatty acids containing at least 8 and, more particularly, B to 22 carbon atoms are condensed with 2-aminoethanol in the presence of titanium or zirconium compounds corresponding to general formula II
M(OR2) 4 (II) in which M represents tetravalent titanium or zirconium and R2 is an alkyl group containing at least 2 and more par-ticularly 2 to 4 carbon atoms, an acyl group containing at least 2 and more particularly 2 to 10 carbon atoms or a 2-aminoethyleneoxy group or the residue of a B-diketone corresponding to general formula III
R3-C=CH-Co-R4 (III) in which .. ~ .
"'. . ' ' ' . ' ' ' ' ~;3~
W0 90/135~5 3 PC~/EPgO/006~9 R3 and R4 may be the same or different and represent radicals from the group consisting of alkyl yroups contain-ing 1 to 4 carbon atoms and phenyl optionally substituted in the p-position, two of the groups R2 together being formed by the two~bond radical of a dihydric alcohol containing 2 to 4 carbon atoms in the presence of titanyl acetyl acetonate or in the presence of condensation products of titanium(IV) or zirconium(IV) tetraalkoxylates corresponding to general formula II, in which M and R2 are as defined above, with polyfunctional alkanols, more particularly containing 3 to 12 carbon atoms and 2 to 6 hydroxyl groups, and the 2-alkyl or 2-alkenyloxazolines thus obtained are isolated with removal of water and glycerol formed.
The process according to the invention may be applied inter alia to any fatty acid glycerides derived from straight-chain or branched, saturated or unsaturated fatty acids containing at least 8 carbon atoms, more particularly 8 to 22 carbon atoms, including hydroxy-substituted deriva-tives thereof. Preferred starting compounds for the process according to the invention are fatty acid glycer-ides, more particularly triglycerides, of vegetable, animal or sea-animal origin, including technical mixtures thereof and derivatives hardened by catalytic hydrogenation.
Typical representatives of the fatty acids occurring in the glycerides mentioned above are caprylic, capric, myristic, palmitic, stearic, 12-hydroxystearic, arachic, behenic, lignoceric, lauroleic, myristoleic, palmitoleic, oleic, gadoleic, erucic, ricinoleic, linoleic, linolenic and arachidonic acid. As usual in oleoc~emistry, the fatSy acid glycerides are not generally used as such, but in the form of technical mixtures of the type obtainable from natural raw materials, for example ~rom lauric oils, coconut oil, palm oil, palm kexnel oil, soybean oil, peanut ~3~37~i oil, rapeseed oil, olive oil, linseed oil, sunflower oil, castor oil, beef tallow, lard and fish oil.
The titanium or zirconium compounds suitable for use as catalysts in the process according to the invention are known and, for the most part, are commercially available.
Condensation products of titanium(IV) or zirconium(IV) tetraalkoxylates with polyfunctional alkanols containing 3 to 12 carbon atoms and 2 to 6 hydroxyl groups, such as glycerol, trimethylol propane and pentaerythritol, are esterification and/or transesterification catalysts, which are described for example in US-C 4,705,764, to which reference is hereby made. Another suitable polyalkanol is polyvinyl alcohol. The titanium or zirconium tetra-(2-aminoethoxylates) also suitable as catalysts may be prepar-ed from titanium or zirconium tetraalkoxylates and 2-amino-ethanol.
In one preferred embodiment of the invention, esters of titanic acid (H4Tio4) or zirconic acid (H4ZrO4) or mixed anhydrides of titanic or zirconic acid with organic acids corresponding to general formula II, in which M = Ti or zr and R2 is an alkyl group containing at least 2 or more than 2 carbon atoms and more particularly 2 to 4 carbon atoms or an acyl group containing 2 or more than 2 carbon atoms, more particularly 2 to 10 carbon atoms, derived from a monocarboxylic acid, are used as catalysts.
In another advantageous embodiment of the invention, catalysts from the group consisting of titanium or zir-conium tetraethylate, tetrapropylate, tetraisopropylate, tetrabutylate and tetraacetate are used.
In another advantageous embodiment of the invention, titanium or zirconium acetyl acetonates corresponding to general formula (IV) (R50) mM (ACA) n ( IV) .
'-.- . , : . , -' ' . - " ' ~5~37~
WO 90/1354S 5 PCT/~P~o/00629 in which R5 is an alkyl group containing 1 to 4 carbon atoms, ACA is an acetyl acetonate group and m is the number 0 and n is the number ~ or m is the number 2 and n is the number 2, are used as catalysts.
In another advantageous embodiment of the invention, polycondensation products of esters of titanic acid with monoalkanols containing 2 to 10 carbon atoms with penta-erythritol are used as catalysts.
In another advantageous embodiment of the invention, the catalysts to be used in accsrdance with the invention are used in a quantity of 0.1 to 10 mol-% and preferably in a quantity of 1 to 5 mol-%, based on the fatty acid resi-dues present.
According to the invention, the condensation reaction is carried out at 150 to 270C, preferably in vacuo and in an inert gas atmosphere. The water of reaction formed may be distilled off together with the 2-alkyl or alkenyl-substituted 2-oxazolines and separated therefrom during the distillation, entrained residual water being removed with typical drying agents, such as anhydrous sodium sulfate or molecular sieve (4A), particularly in the case of relative-ly short-chain 2-alkyl or alkenyl-2-oxazolines. However, the water of reaction may also be removed from the reaction mixture before the actual distillation of the 2-oxazolines by azeotropic distillation with high boiling entraining agents, such as for example tetralin or cumene.
In another preferred embodiment of the invention, the 2-alkyl or alkenyl-substituted 2-oxazolines may be directly prepared from fatty acid glycerides by reaction thereof at elevated temperature and at atmospheric pressure in the presence of ethanolamine to form the fatty acid ethanol-amides, removing water and glycerol formed and any un-reacted or excess ethanolamine substantially completely by distillation in vacuo and leaving the reaction mixture to 3~37~
react ln vacuo in a second step in which the reaction temperature is further increased. The glycerides react in the presence of ethanolamine and the claimed catalysts in a first step to form fatty acid ethanolamides which react in the second step to form the 2-oxazolines. The ethanol-amine is preferably usPd in a 50 to 400 mol-% excess, based on the starting material. A reaction temperature below 185C is preferably applied in the first step, a reaction temperature of 185 to 270C preferably being applied in the second step. The catalysts are preferably used in a quan-tity of 0.1 to 10 mol-% and preferably in a quantity of 1 to 5 mol-%, based on the fatty acid residues present.
Titanium tetraalcoholates, more particularly selected from the group consisting of titanium tetraethylate, propylate, isopropylate and butylate, are again preferably used.
Alternatively, mixed anhydrides of titanic acid with monocarboxylic acids, particularly those containing 1 to 4 carbon atoms, preferably titanium tetraacetate, are used.
Other preferred catalysts are titanium or zirconium acetyl acetonates corresponding to general formula IV, the above-mentioned polycondensation products of esters of titanic acid with monoalkanols containing 2 to 10 carbon atoms with pentaerythritol and also titanium(IV) or Zr(IVJ tetraamino-ethanolates.
In this variant of the process, the second reaction step is preferably carried out in vacuo and the water of reaction formed is distilled off together with the 2-alkyl or alkenyl-substituted 2-oxazolines with further separation during distillation. However, the water of reaction may also be removed by azeotropic distillation before distilla-tion of the 2-alkyl or alkenyl-2-oxazolines.
It is of particular advantage in this regard to carry out the first and the second stages of the reaction as a one-pot reaction in one and the same reactor.
The invention is illustrated by the following Ex-amples.
~3~37~
WO 90/135~5 7 PC~/EP90/00629 Example 1.
Preparation of 2~fatty alkenyl-2-oxazoline from soybean oil A mixture of 295 g (0.333 mol) soybean oil, degummed, hydroxyl value 2.3, iodine value 128.6, saponification value 193.8, acid value 0.5 123 g (2 mol) ethanolamine (99.5~), 3.4 g (0.01 mol, 3 mol-%) titanium tetrabutylate was introduced into a stirred reactor equipped with a fractionating column, a descending condenser with distilla-tion receivers, a vacuum source with a cold trap ~or the water of reaction, a thermometer and an inlet pipe for inert gas.
After 4 hours' refluxing under nitrogen at normal pressure, the excess ethanolamine was distilled off in vacuo at 81 to 87C/20 hPa. The glycerol formed was then distilled off in vacuo at 144 to 182C/0.8 to 0.1 hPa.
The soybean oil fatty acid ethanolamide thus obtained was heated in vacuo to 194 to 268C, the 2-soybean oil fatty alkenyl-2-oxazoline and water distilling over simul-taneously at 160 to 194C/0.07 hPa. Most of the water was condensed in the cold trap. To free the oxaæoline dis-tilled over from any water entrained, sodium sulfate was introduced as drying agent into the distillation receivers.
2-Soybean oil fatty alkenyl-2-oxazoline was obtained in a yield of 241.6 g (79% of the theoretical, based on the soybean oil used~.
IR: 1671 (C=N): 1230, 1171 (C-O-C=~; 989, 953, 915 cm (oxazoline~
Example 2.
Preparation of 2-fatty alkenyl-2-oxazoline from soybean oil Refined soybean oil was reacted with ethanolamine by the method described in Example 1 to ~orm 2-soybean oil fatty alkenyl-2-oxazoline. The following quantitie~ were 2~
WO 90/135~5 8 PCT~EP90/00629 used:
443 g (0.50 mol) soybean oil, re~ined, hydroxyl value 0.0, iodine value 127.5, saponi~ication value 193.0, acid value 0.2 184.2 g (3 mol) ethanolamine (99.5%) 5.1 g (0.015 mol, 1 mol-%) titanium tetrabutylate Yield: 351.8 g (77~ of the theoretical) Bp. = 178 to 200C (0.06 hPa) IR: 1670, (C=N); 1231, 1170 (C-0-C=); 989, 953, 915 cm (oxazoline);
lH-NMR: delta (in ppm)= 5.35 (ca. 3H,m), 4.21 (2H,t,J = 7 Hz), 3.82 (2H,t,J = 6 Hz), 2.77 (ca. 1.5H,br,t,J= 5 Hz), 2.25 (2H,t,J= 6 Hz), 2.04 (4H,m), 1.63 (2H,p,J= 6 Hz), 1.29 (ca. 18H,m), 0.88 (3H,t,J = 6 Hz), 0.89 (3H,t,J = 6 Hz).
Example 3.
Preparation of 2-tallow alkyl-2-oxazoline from hydrogenated tallow.
Hydrogenated tallow was reacted with ethanolamine by the method described in Example 1. The ~ollowing quan-tities were used:
428 g (0.50 mol) beef tallow, hydrogenated, commercial quality, iodine value 0.1, saponification value 196.7, acid value 2.8, Mp. 57-5Ct fatty acid distribution: approx. 28%
Cl6, approx- 70% Cl8;
184.2 g (3 mol) ethanolamine (99.5%) 5.1 g (0.015 mol, 1 mol-%) titanium tetrabutylate.
Yield: 371.0 g (83~ of the theoretical) Bp. = 188 to 210C (0.04 to 0.08 hPa) IR: 1670 (C=N): 1231, 1170 (C-0-C=); 988, 954, 915 cm (oxazoline) lH-NMR: delta (in ppm)= 4.22 (2H,t,J = 7 Hz), 3.82 (2H,t,J
= 7 Hz), 2.27 (2H,t,J = 6 Hz), 1.63 (2H,p,J = 6 Hz~, 1.24 (ca. 28H,m), 0.89 (3H,t,J = 6 Hz) Example 4.
Preparation of 2~ hydroxyheptadecyl)-2-oxazoline ~rom hydrogenated castor oil A commercial hydrogenated castor oil was reacted with ethanolamine hy the method described in Example 1. The following quantities ~ere used:
473 g (0.5 mol) castor oil, hydrogenated, saponification value 1~8.7, acid value 0.2 184.2 g (3 mol) ethanolamine (99.5%) 15.3 g (0.045 mol, 3 mol-%) titanium tetrabutylate Yield = 371 g 2~ hydroxyheptadecyl)-2-oxazoline.
Bp. = 214 to 223C (0.3 to 0.7 hPa) IR: 3295 (OH); 1671, (C=N), 1172 (C-O-C=); 1134, 992, 962, 923 cm~1 (oxazoline).
lH-NMR: delta (in ppm)= 5.4 (ca. 0.25 H,m), 4.22 (2H,t,J =
7Hz), 3.83 (2Ht,J = 7 Hz), 3.58 (ca. 0.75 H,m), 2.26 (2H,t,J = 6 Hz), 1.98 (ca. 0.5 H,m), 1.63 (2H,m), 1.24 (caO
16 H,m), 0.89 (3H,t,J = 6 Hz).
Example 5.
Preparation of 2-(soybean oil fatty alkenyl)-2-oxazoline from refined soybean oil Using the method described in Example 1, refined soybean oil was reacted with ethanolamine in the presence of zirconium tetrabutylate to form 2-(11-hydroxyhepta-decyl)-2-oxazoline. The following quantities were used:
434.2 g (0.5 mol) soybean oil, degummed; S.V. = 193.8 184.2 g (3.0 mol) ethanolamine (99.5%) 5.8 g (0.015 mol, 1 mol-%, based on the fatty acid residues used~ zirconium tetrabutylate Yield = 264 g (58% of the theoretical) 2-(soybean oil fatty alkenyl)-2-oxazoline.
Bp. = 187 - 219C (0.05 - 0.1 hPa) The lH-NMR and IR spectra were in accordance with the structure.
;~5~
Example 6.
Preparation of 2-(rapeseed oil fatty al~yl)-2-oxazoline from rapeseed oil.
Rapeseed oil, in which approximately 40~ of the ~atty acid component consists of erucic acid, was reacted with ethanolamine by the method of Example 1 to form 2-rapeseed oil fatty alkyl)-2-oxazoline. The following quantities were used:
474.0 g (approx. 0.5 mol) rapeseed oil; S.V. = 175 184.0 g (3.0 mol) ethanolamine (99.5%) 15.3 g (0.045 mol, 3 mol-%, based on the fatty acid resi-dues used) titanium tetrabutylate Yield = 353 g (73% of the theoretical) 2-(rapeseed oil fatty alkyl)-2-oxazoline.
Bp. = 202 - 230C (0.01 - 0.05 hPa) IR: 1670 (C=N); 1231, 1171 (C-O-C=); 989, 953, 315 cm (oxazoline).
lH-NMR: delta (in ppm) 5.36 (ca. 2.5H,m); 4.20 (2H,t,J = 6 Hz); 3.71 (2H,t,J, = 6 Hz); 2.70 ~<lH,m); 2.24 (2H,t,J = 6 Hz); 2.02 (ca. 4H,m); 1063 (2H,br p,J - 6 Hz); 1.26 (ca.
24H, br s); 0.88 (3H,t,J = 5 Hz).
Example 7.
Preparation of 2-(soyabean oil fatty alkenyl)-2-oxazoline from degummed soybean oil Using the method described in Example 1, degummed soybean oil was reacted with ethanolamine in the presence of titanium(IV) diisopropoxy bis-acetyl acetonate to form 2-(soybean oil fatty alkenyl)-2-oxazoline. The following quantities were used:
434.2 g (0.5 mol) soybean oil, degummed; S.V. = 193.8 184.2 g (3.0 mol) ethanolamine (99.5%) 5.5 g (0.015 mol, 1 mol-% based on the fatty acid residues used) titanium(IV) diisopropoxy~bis-acetyl acetonate Yield = 359.4 g (80% of the theoretical) 2-(soybean oil `
~3~37~
~0 90~13545 11 PCT/EPgo/00629 fatty alkenyl)-2-oxazoline.
Bp. = 187 - 200C (0.1 hPa).
The lH-NMR and IR spectra were in accordance with the structure.
Example 8.
Preparation of 2-(soybean oil fatty alkenyl)-2-oxaæoline from degummed soybean oil Using the method described in Example 1 degummed soybean oil was reacted with ethanolamine in the presence of zirconium acetyl acetonate to form 2-(soybean oil fatty alkenyl)-2-oxazoline. The following quantities were used:
434.2 g (0.5 mol) soybean oil, degummed; S.V. = 193.8 184.2 g (3.0 mol) ethanolamine, 99.5%
7.3 g (0.015 mol, 1 mol-%, based on the fatty acid residues used) zirconium acetyl acetonate.
Yield: 334 g (74% of the theoretical) 2-(soybean oil fatty alkenyl)-2-oxazoline.
Bp. = 234 - 212C (0.1 hPa) The lH-NMR and IR were in accordance with the struc-ture.
' ' , ` ' :: ,
The most simple method is based on the cyclodehydra-tion of N-2-hydroxyethyl carboxylic acid amides (Chem. Rev.
44, 447 et ~g (1949), Chem. Rev. 71, 485 et ~g (1971)).
However, cyclization of the unsubstituted N-2-hydroxyethyl carboxylic acid amides requires very drastic conditions or the presence of special cataly~ts. Whereas gas-phase reac-tions in the presence of dehydrating metal oxides, such as Al203, SiOJAl2O3, Al2O3/TiO2, Tio2 or MgO, have proved to be s~itable for the preparation of readily volatile, short-c:hain 2-alkyl-2-oxazolines, the more volatile, relatively ; 30 long-chain 2-alkyl-2-oxazolines are better prepared in the liguid phase, Compounds of manganese, cobalt, molybdenum, X~5~37~
W0 90/13545 2 PC~/EP90/00629 tungsten, iron, cadmium, zinc and tin and also compounds of the rare earth metals have been described as catalysts for the liquid-phase reaction (cf. US-PS 3,562,263, BE-PS 666 829, C.A. 87, 135353, C.A. 87, 135352, US-PS 3,681,329, US-PS 3,681,333, EP-OS 0 033 752, US-PS 4,543,414, US~PS
4,354,029, US-PS 4,443,611, EP-OS 0 105 944 and EP-05 0 164 219)~ However, the catalysts described in the publications cited above do not lead to good yields in the production of relatively long-chain 2-fatty alkyl-2-oxazolines.
It has now been found that special titanium and zirconium compounds are eminently suitable as catalysts for a process of the type mentioned at the beginning, enabling yields of up to about 85~ of the theoretical, based on the starting compound, to be obtained.
Accordingly, the present invention relates to a process of the type mentioned at the beginning in which glycerides, more particularly triglycerides, of optionally hydroxy-substituted fatty acids containing at least 8 and, more particularly, B to 22 carbon atoms are condensed with 2-aminoethanol in the presence of titanium or zirconium compounds corresponding to general formula II
M(OR2) 4 (II) in which M represents tetravalent titanium or zirconium and R2 is an alkyl group containing at least 2 and more par-ticularly 2 to 4 carbon atoms, an acyl group containing at least 2 and more particularly 2 to 10 carbon atoms or a 2-aminoethyleneoxy group or the residue of a B-diketone corresponding to general formula III
R3-C=CH-Co-R4 (III) in which .. ~ .
"'. . ' ' ' . ' ' ' ' ~;3~
W0 90/135~5 3 PC~/EPgO/006~9 R3 and R4 may be the same or different and represent radicals from the group consisting of alkyl yroups contain-ing 1 to 4 carbon atoms and phenyl optionally substituted in the p-position, two of the groups R2 together being formed by the two~bond radical of a dihydric alcohol containing 2 to 4 carbon atoms in the presence of titanyl acetyl acetonate or in the presence of condensation products of titanium(IV) or zirconium(IV) tetraalkoxylates corresponding to general formula II, in which M and R2 are as defined above, with polyfunctional alkanols, more particularly containing 3 to 12 carbon atoms and 2 to 6 hydroxyl groups, and the 2-alkyl or 2-alkenyloxazolines thus obtained are isolated with removal of water and glycerol formed.
The process according to the invention may be applied inter alia to any fatty acid glycerides derived from straight-chain or branched, saturated or unsaturated fatty acids containing at least 8 carbon atoms, more particularly 8 to 22 carbon atoms, including hydroxy-substituted deriva-tives thereof. Preferred starting compounds for the process according to the invention are fatty acid glycer-ides, more particularly triglycerides, of vegetable, animal or sea-animal origin, including technical mixtures thereof and derivatives hardened by catalytic hydrogenation.
Typical representatives of the fatty acids occurring in the glycerides mentioned above are caprylic, capric, myristic, palmitic, stearic, 12-hydroxystearic, arachic, behenic, lignoceric, lauroleic, myristoleic, palmitoleic, oleic, gadoleic, erucic, ricinoleic, linoleic, linolenic and arachidonic acid. As usual in oleoc~emistry, the fatSy acid glycerides are not generally used as such, but in the form of technical mixtures of the type obtainable from natural raw materials, for example ~rom lauric oils, coconut oil, palm oil, palm kexnel oil, soybean oil, peanut ~3~37~i oil, rapeseed oil, olive oil, linseed oil, sunflower oil, castor oil, beef tallow, lard and fish oil.
The titanium or zirconium compounds suitable for use as catalysts in the process according to the invention are known and, for the most part, are commercially available.
Condensation products of titanium(IV) or zirconium(IV) tetraalkoxylates with polyfunctional alkanols containing 3 to 12 carbon atoms and 2 to 6 hydroxyl groups, such as glycerol, trimethylol propane and pentaerythritol, are esterification and/or transesterification catalysts, which are described for example in US-C 4,705,764, to which reference is hereby made. Another suitable polyalkanol is polyvinyl alcohol. The titanium or zirconium tetra-(2-aminoethoxylates) also suitable as catalysts may be prepar-ed from titanium or zirconium tetraalkoxylates and 2-amino-ethanol.
In one preferred embodiment of the invention, esters of titanic acid (H4Tio4) or zirconic acid (H4ZrO4) or mixed anhydrides of titanic or zirconic acid with organic acids corresponding to general formula II, in which M = Ti or zr and R2 is an alkyl group containing at least 2 or more than 2 carbon atoms and more particularly 2 to 4 carbon atoms or an acyl group containing 2 or more than 2 carbon atoms, more particularly 2 to 10 carbon atoms, derived from a monocarboxylic acid, are used as catalysts.
In another advantageous embodiment of the invention, catalysts from the group consisting of titanium or zir-conium tetraethylate, tetrapropylate, tetraisopropylate, tetrabutylate and tetraacetate are used.
In another advantageous embodiment of the invention, titanium or zirconium acetyl acetonates corresponding to general formula (IV) (R50) mM (ACA) n ( IV) .
'-.- . , : . , -' ' . - " ' ~5~37~
WO 90/1354S 5 PCT/~P~o/00629 in which R5 is an alkyl group containing 1 to 4 carbon atoms, ACA is an acetyl acetonate group and m is the number 0 and n is the number ~ or m is the number 2 and n is the number 2, are used as catalysts.
In another advantageous embodiment of the invention, polycondensation products of esters of titanic acid with monoalkanols containing 2 to 10 carbon atoms with penta-erythritol are used as catalysts.
In another advantageous embodiment of the invention, the catalysts to be used in accsrdance with the invention are used in a quantity of 0.1 to 10 mol-% and preferably in a quantity of 1 to 5 mol-%, based on the fatty acid resi-dues present.
According to the invention, the condensation reaction is carried out at 150 to 270C, preferably in vacuo and in an inert gas atmosphere. The water of reaction formed may be distilled off together with the 2-alkyl or alkenyl-substituted 2-oxazolines and separated therefrom during the distillation, entrained residual water being removed with typical drying agents, such as anhydrous sodium sulfate or molecular sieve (4A), particularly in the case of relative-ly short-chain 2-alkyl or alkenyl-2-oxazolines. However, the water of reaction may also be removed from the reaction mixture before the actual distillation of the 2-oxazolines by azeotropic distillation with high boiling entraining agents, such as for example tetralin or cumene.
In another preferred embodiment of the invention, the 2-alkyl or alkenyl-substituted 2-oxazolines may be directly prepared from fatty acid glycerides by reaction thereof at elevated temperature and at atmospheric pressure in the presence of ethanolamine to form the fatty acid ethanol-amides, removing water and glycerol formed and any un-reacted or excess ethanolamine substantially completely by distillation in vacuo and leaving the reaction mixture to 3~37~
react ln vacuo in a second step in which the reaction temperature is further increased. The glycerides react in the presence of ethanolamine and the claimed catalysts in a first step to form fatty acid ethanolamides which react in the second step to form the 2-oxazolines. The ethanol-amine is preferably usPd in a 50 to 400 mol-% excess, based on the starting material. A reaction temperature below 185C is preferably applied in the first step, a reaction temperature of 185 to 270C preferably being applied in the second step. The catalysts are preferably used in a quan-tity of 0.1 to 10 mol-% and preferably in a quantity of 1 to 5 mol-%, based on the fatty acid residues present.
Titanium tetraalcoholates, more particularly selected from the group consisting of titanium tetraethylate, propylate, isopropylate and butylate, are again preferably used.
Alternatively, mixed anhydrides of titanic acid with monocarboxylic acids, particularly those containing 1 to 4 carbon atoms, preferably titanium tetraacetate, are used.
Other preferred catalysts are titanium or zirconium acetyl acetonates corresponding to general formula IV, the above-mentioned polycondensation products of esters of titanic acid with monoalkanols containing 2 to 10 carbon atoms with pentaerythritol and also titanium(IV) or Zr(IVJ tetraamino-ethanolates.
In this variant of the process, the second reaction step is preferably carried out in vacuo and the water of reaction formed is distilled off together with the 2-alkyl or alkenyl-substituted 2-oxazolines with further separation during distillation. However, the water of reaction may also be removed by azeotropic distillation before distilla-tion of the 2-alkyl or alkenyl-2-oxazolines.
It is of particular advantage in this regard to carry out the first and the second stages of the reaction as a one-pot reaction in one and the same reactor.
The invention is illustrated by the following Ex-amples.
~3~37~
WO 90/135~5 7 PC~/EP90/00629 Example 1.
Preparation of 2~fatty alkenyl-2-oxazoline from soybean oil A mixture of 295 g (0.333 mol) soybean oil, degummed, hydroxyl value 2.3, iodine value 128.6, saponification value 193.8, acid value 0.5 123 g (2 mol) ethanolamine (99.5~), 3.4 g (0.01 mol, 3 mol-%) titanium tetrabutylate was introduced into a stirred reactor equipped with a fractionating column, a descending condenser with distilla-tion receivers, a vacuum source with a cold trap ~or the water of reaction, a thermometer and an inlet pipe for inert gas.
After 4 hours' refluxing under nitrogen at normal pressure, the excess ethanolamine was distilled off in vacuo at 81 to 87C/20 hPa. The glycerol formed was then distilled off in vacuo at 144 to 182C/0.8 to 0.1 hPa.
The soybean oil fatty acid ethanolamide thus obtained was heated in vacuo to 194 to 268C, the 2-soybean oil fatty alkenyl-2-oxazoline and water distilling over simul-taneously at 160 to 194C/0.07 hPa. Most of the water was condensed in the cold trap. To free the oxaæoline dis-tilled over from any water entrained, sodium sulfate was introduced as drying agent into the distillation receivers.
2-Soybean oil fatty alkenyl-2-oxazoline was obtained in a yield of 241.6 g (79% of the theoretical, based on the soybean oil used~.
IR: 1671 (C=N): 1230, 1171 (C-O-C=~; 989, 953, 915 cm (oxazoline~
Example 2.
Preparation of 2-fatty alkenyl-2-oxazoline from soybean oil Refined soybean oil was reacted with ethanolamine by the method described in Example 1 to ~orm 2-soybean oil fatty alkenyl-2-oxazoline. The following quantitie~ were 2~
WO 90/135~5 8 PCT~EP90/00629 used:
443 g (0.50 mol) soybean oil, re~ined, hydroxyl value 0.0, iodine value 127.5, saponi~ication value 193.0, acid value 0.2 184.2 g (3 mol) ethanolamine (99.5%) 5.1 g (0.015 mol, 1 mol-%) titanium tetrabutylate Yield: 351.8 g (77~ of the theoretical) Bp. = 178 to 200C (0.06 hPa) IR: 1670, (C=N); 1231, 1170 (C-0-C=); 989, 953, 915 cm (oxazoline);
lH-NMR: delta (in ppm)= 5.35 (ca. 3H,m), 4.21 (2H,t,J = 7 Hz), 3.82 (2H,t,J = 6 Hz), 2.77 (ca. 1.5H,br,t,J= 5 Hz), 2.25 (2H,t,J= 6 Hz), 2.04 (4H,m), 1.63 (2H,p,J= 6 Hz), 1.29 (ca. 18H,m), 0.88 (3H,t,J = 6 Hz), 0.89 (3H,t,J = 6 Hz).
Example 3.
Preparation of 2-tallow alkyl-2-oxazoline from hydrogenated tallow.
Hydrogenated tallow was reacted with ethanolamine by the method described in Example 1. The ~ollowing quan-tities were used:
428 g (0.50 mol) beef tallow, hydrogenated, commercial quality, iodine value 0.1, saponification value 196.7, acid value 2.8, Mp. 57-5Ct fatty acid distribution: approx. 28%
Cl6, approx- 70% Cl8;
184.2 g (3 mol) ethanolamine (99.5%) 5.1 g (0.015 mol, 1 mol-%) titanium tetrabutylate.
Yield: 371.0 g (83~ of the theoretical) Bp. = 188 to 210C (0.04 to 0.08 hPa) IR: 1670 (C=N): 1231, 1170 (C-0-C=); 988, 954, 915 cm (oxazoline) lH-NMR: delta (in ppm)= 4.22 (2H,t,J = 7 Hz), 3.82 (2H,t,J
= 7 Hz), 2.27 (2H,t,J = 6 Hz), 1.63 (2H,p,J = 6 Hz~, 1.24 (ca. 28H,m), 0.89 (3H,t,J = 6 Hz) Example 4.
Preparation of 2~ hydroxyheptadecyl)-2-oxazoline ~rom hydrogenated castor oil A commercial hydrogenated castor oil was reacted with ethanolamine hy the method described in Example 1. The following quantities ~ere used:
473 g (0.5 mol) castor oil, hydrogenated, saponification value 1~8.7, acid value 0.2 184.2 g (3 mol) ethanolamine (99.5%) 15.3 g (0.045 mol, 3 mol-%) titanium tetrabutylate Yield = 371 g 2~ hydroxyheptadecyl)-2-oxazoline.
Bp. = 214 to 223C (0.3 to 0.7 hPa) IR: 3295 (OH); 1671, (C=N), 1172 (C-O-C=); 1134, 992, 962, 923 cm~1 (oxazoline).
lH-NMR: delta (in ppm)= 5.4 (ca. 0.25 H,m), 4.22 (2H,t,J =
7Hz), 3.83 (2Ht,J = 7 Hz), 3.58 (ca. 0.75 H,m), 2.26 (2H,t,J = 6 Hz), 1.98 (ca. 0.5 H,m), 1.63 (2H,m), 1.24 (caO
16 H,m), 0.89 (3H,t,J = 6 Hz).
Example 5.
Preparation of 2-(soybean oil fatty alkenyl)-2-oxazoline from refined soybean oil Using the method described in Example 1, refined soybean oil was reacted with ethanolamine in the presence of zirconium tetrabutylate to form 2-(11-hydroxyhepta-decyl)-2-oxazoline. The following quantities were used:
434.2 g (0.5 mol) soybean oil, degummed; S.V. = 193.8 184.2 g (3.0 mol) ethanolamine (99.5%) 5.8 g (0.015 mol, 1 mol-%, based on the fatty acid residues used~ zirconium tetrabutylate Yield = 264 g (58% of the theoretical) 2-(soybean oil fatty alkenyl)-2-oxazoline.
Bp. = 187 - 219C (0.05 - 0.1 hPa) The lH-NMR and IR spectra were in accordance with the structure.
;~5~
Example 6.
Preparation of 2-(rapeseed oil fatty al~yl)-2-oxazoline from rapeseed oil.
Rapeseed oil, in which approximately 40~ of the ~atty acid component consists of erucic acid, was reacted with ethanolamine by the method of Example 1 to form 2-rapeseed oil fatty alkyl)-2-oxazoline. The following quantities were used:
474.0 g (approx. 0.5 mol) rapeseed oil; S.V. = 175 184.0 g (3.0 mol) ethanolamine (99.5%) 15.3 g (0.045 mol, 3 mol-%, based on the fatty acid resi-dues used) titanium tetrabutylate Yield = 353 g (73% of the theoretical) 2-(rapeseed oil fatty alkyl)-2-oxazoline.
Bp. = 202 - 230C (0.01 - 0.05 hPa) IR: 1670 (C=N); 1231, 1171 (C-O-C=); 989, 953, 315 cm (oxazoline).
lH-NMR: delta (in ppm) 5.36 (ca. 2.5H,m); 4.20 (2H,t,J = 6 Hz); 3.71 (2H,t,J, = 6 Hz); 2.70 ~<lH,m); 2.24 (2H,t,J = 6 Hz); 2.02 (ca. 4H,m); 1063 (2H,br p,J - 6 Hz); 1.26 (ca.
24H, br s); 0.88 (3H,t,J = 5 Hz).
Example 7.
Preparation of 2-(soyabean oil fatty alkenyl)-2-oxazoline from degummed soybean oil Using the method described in Example 1, degummed soybean oil was reacted with ethanolamine in the presence of titanium(IV) diisopropoxy bis-acetyl acetonate to form 2-(soybean oil fatty alkenyl)-2-oxazoline. The following quantities were used:
434.2 g (0.5 mol) soybean oil, degummed; S.V. = 193.8 184.2 g (3.0 mol) ethanolamine (99.5%) 5.5 g (0.015 mol, 1 mol-% based on the fatty acid residues used) titanium(IV) diisopropoxy~bis-acetyl acetonate Yield = 359.4 g (80% of the theoretical) 2-(soybean oil `
~3~37~
~0 90~13545 11 PCT/EPgo/00629 fatty alkenyl)-2-oxazoline.
Bp. = 187 - 200C (0.1 hPa).
The lH-NMR and IR spectra were in accordance with the structure.
Example 8.
Preparation of 2-(soybean oil fatty alkenyl)-2-oxaæoline from degummed soybean oil Using the method described in Example 1 degummed soybean oil was reacted with ethanolamine in the presence of zirconium acetyl acetonate to form 2-(soybean oil fatty alkenyl)-2-oxazoline. The following quantities were used:
434.2 g (0.5 mol) soybean oil, degummed; S.V. = 193.8 184.2 g (3.0 mol) ethanolamine, 99.5%
7.3 g (0.015 mol, 1 mol-%, based on the fatty acid residues used) zirconium acetyl acetonate.
Yield: 334 g (74% of the theoretical) 2-(soybean oil fatty alkenyl)-2-oxazoline.
Bp. = 234 - 212C (0.1 hPa) The lH-NMR and IR were in accordance with the struc-ture.
' ' , ` ' :: ,
Claims (13)
1. A process for the production of 2-alkyl or alkenyl-2-oxazolines corresponding to general formula I
(I) in which R1 is an optionally hydroxy-substituted hydrocarbon radical containing at least 7 and, more particularly, 7 to 21 carbon atoms in the hydrocarbon chain, by condensation of fatty acid ethanolamides or fatty acid glycerides and 2-aminoethanol as precursors thereof in the liquid phase in the presence of catalysts, characterized in that glycerides, more particularly triglycerides, of optionally hydroxy-substituted fatty acids containing at least 8 and, more particularly, 8 to 22 carbon atoms are condensed with 2-aminoethanol in the presence of titanium or zirconium compounds corresponding to general formula II
(II) in which M represents tetravalent titanium or zirconium and R2 is an alkyl group containing at least 2 and more par-ticularly 2 to 4 carbon atoms, an acyl group containing at least 2 and more particularly 2 to 10 carbon atoms or a 2-aminoethyleneoxy group or the residue of a .beta.-diketone corresponding to general formula III
(III) in which R3 and R4 may be the same or different and represent radicals from the group consisting of alkyl groups contain-ing 1 to 4 carbon atoms and phenyl optionally substituted in the p-position, two of the groups R2 together being formed by the two-bond radical of a dihydric alcohol containing 2 to 4 carbon atoms in the presence of titanyl acetyl acetonate or in the presence of condensation products of titanium(IV) or zirconium(IV) tetraalkoxylates corresponding to general formula II, in which M and R2 are as defined above, with polyfunctional alkanols, more particularly containing 3 to 12 carbon atoms and 2 to 6 hydroxyl groups, and the 2-alkyl or 2-alkenyloxazolines thus obtained are isolated with removal of water and glycerol formed.
(I) in which R1 is an optionally hydroxy-substituted hydrocarbon radical containing at least 7 and, more particularly, 7 to 21 carbon atoms in the hydrocarbon chain, by condensation of fatty acid ethanolamides or fatty acid glycerides and 2-aminoethanol as precursors thereof in the liquid phase in the presence of catalysts, characterized in that glycerides, more particularly triglycerides, of optionally hydroxy-substituted fatty acids containing at least 8 and, more particularly, 8 to 22 carbon atoms are condensed with 2-aminoethanol in the presence of titanium or zirconium compounds corresponding to general formula II
(II) in which M represents tetravalent titanium or zirconium and R2 is an alkyl group containing at least 2 and more par-ticularly 2 to 4 carbon atoms, an acyl group containing at least 2 and more particularly 2 to 10 carbon atoms or a 2-aminoethyleneoxy group or the residue of a .beta.-diketone corresponding to general formula III
(III) in which R3 and R4 may be the same or different and represent radicals from the group consisting of alkyl groups contain-ing 1 to 4 carbon atoms and phenyl optionally substituted in the p-position, two of the groups R2 together being formed by the two-bond radical of a dihydric alcohol containing 2 to 4 carbon atoms in the presence of titanyl acetyl acetonate or in the presence of condensation products of titanium(IV) or zirconium(IV) tetraalkoxylates corresponding to general formula II, in which M and R2 are as defined above, with polyfunctional alkanols, more particularly containing 3 to 12 carbon atoms and 2 to 6 hydroxyl groups, and the 2-alkyl or 2-alkenyloxazolines thus obtained are isolated with removal of water and glycerol formed.
2. A process as claimed in claim 1, characterized in that, esters of titanic acid (H4TiO4) or zirconic acid (H4ZrO4) or mixed anhydrides of titanic or zirconic acid with organic acids corresponding to general formula II, in which M = Ti or Zr and R2 is an alkyl group containing 2 or more than 2 carbon atoms and more particularly 2 to 4 carbon atoms or an acyl group containing 2 or more than 2 carbon atoms, more particularly 2 to 10 carbon atoms, derived from a monocarboxylic acid, are used as catalysts.
3. A process as claimed in claim 1 or 2, characterized in that, catalysts from the group consisting of titanium or zirconium tetraethylate, tetrapropylate, tetraisopropylate, tetrabutylate and tetraacetate are used.
4. A process as claimed in claim 1 or 2, characterized in that tetra(aminoethyl) titanate or zirconate is used as the catalyst.
5. A process as claimed in claim 1 or 2, characterized in that titanium or zirconium acetyl acetonates corresponding to general formula (IV) (IV) in which R5 is an alkyl group containing 1 to 4 carbon atoms, ACA is an acetyl acetonate group and m is the number 0 and n is the number 4 or m is the number 2 and n is the number 2, are used as catalysts.
6. A process as claimed in claim 1 or 2, characterized in that, polycondensation products of esters of titanic acid with monoalkanols containing 2 to 10 carbon atoms with pentaerythritol are used as catalysts.
7. A process as claimed in at least one of claims 1 to 6, characterized in that, the catalysts are used in quantities of 0.1 to 10 mol-% and preferably in quantities of 1 to 5 mol-%, based on the fatty acid residues present.
8. A process as claimed in at least one of claims 1 to 7, characterized in that, in a first step, the fatty acid glycerides are reacted at elevated temperature and at atmospheric pressure in the presence of ethanolamine to form the fatty acid ethanolamides, water and glycerol formed and any unreacted or excess ethanolamine are removed substantially completely by distillation in vacuo and the reaction mixture is left to react in vacuo in a second step in which the reaction temperature is further increased.
9. A process as claimed in claim 8, characterized in that the ethanolamina is used in a 50 to 400 mol-% excess, based on fatty acid residues present in the glycerides.
10. A process as claimed in claim 8 or 9, characterized in that a reaction temperature below 185°C is used in the first step.
11. A process as claimed in at least one of claims 8 to 10, characterized in that a reaction temperature of 185 to 270°C is used in the second step.
12. A process as claimed in at least one of claims 8 to 11, characterized in that 2-oxazoline and water formed in the second step are continuously distilled off and the water is removed from the distillate.
13. A process as claimed in at least one of claims 8 to 12, characterized in that the first and second steps of the reaction are carried out as a one-pot reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893914159 DE3914159A1 (en) | 1989-04-28 | 1989-04-28 | METHOD FOR PRODUCING 2-ALKYL OR ALKENYL-2-OXAZOLINES FROM FATTY ACID GLYCERIDES |
| DEP3914159.4 | 1989-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2053876A1 true CA2053876A1 (en) | 1990-10-29 |
Family
ID=6379734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2053876 Abandoned CA2053876A1 (en) | 1989-04-28 | 1990-04-19 | Process for making 2-alkyl-or alkenyl-2-oxazolines from fatty acid glycerides |
Country Status (6)
| Country | Link |
|---|---|
| EP (2) | EP0470107A1 (en) |
| JP (1) | JPH04504853A (en) |
| BR (1) | BR9007324A (en) |
| CA (1) | CA2053876A1 (en) |
| DE (1) | DE3914159A1 (en) |
| WO (1) | WO1990013545A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6031031A (en) * | 1997-09-10 | 2000-02-29 | Basf Aktiengesellschaft | Thermoplastic molding compositions based on polyesters and polycarbonate |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4313511A1 (en) * | 1993-04-24 | 1994-10-27 | Henkel Kgaa | Batch process for the preparation of oxazolines and oxazines |
| EP0757062B1 (en) * | 1995-08-01 | 2000-02-23 | BASF Aktiengesellschaft | 2-Oxazolinyl terminated polymers and oligomers and use thereof as compatibilizers |
| JPH09124913A (en) | 1995-11-06 | 1997-05-13 | Nippon G Ii Plast Kk | Polyphenylene ether resin composition |
| DE19603304C2 (en) * | 1996-01-25 | 1999-09-09 | Inventa Ag | Use of oxazoline compounds as an activator for triggering the anionic lactam polymerization |
| JP7405015B2 (en) * | 2020-06-22 | 2023-12-26 | 日油株式会社 | Wax thermal response improver and wax composition containing same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1067437B (en) * | 1956-05-11 | 1959-10-22 | Rohm & Haas Company, Philadelphia, Pa. (V. St. A.) | Process for the preparation of 4,4-dialkyl-2vinyl- and 4,4-dialkyl-2-isopropenylsu'bstituierten oxazolines and 5,6-dihydro-4H! -1,3-oχ3zinen and their spirans |
| US3681329A (en) * | 1970-05-04 | 1972-08-01 | Allied Chem | Process for the preparation of cyclic iminoethers |
| DE3824982A1 (en) * | 1987-11-10 | 1989-05-18 | Henkel Kgaa | 2- (11-HYDROXY-8-HEPTADECENYL- OR 11,8- AND 11,9-HEPTADECADIENYL) OXAZOLIN, AND METHOD FOR THE MANUFACTURE, IF SUCH, OF SUBSTITUTED HOEHERER 2- (ALKYL- AND ALKENYL) -OXAZOLINES |
-
1989
- 1989-04-28 DE DE19893914159 patent/DE3914159A1/en not_active Withdrawn
-
1990
- 1990-04-19 JP JP50597790A patent/JPH04504853A/en active Pending
- 1990-04-19 BR BR909007324A patent/BR9007324A/en not_active Application Discontinuation
- 1990-04-19 EP EP19900906193 patent/EP0470107A1/en not_active Withdrawn
- 1990-04-19 EP EP90107492A patent/EP0394854A1/en not_active Withdrawn
- 1990-04-19 WO PCT/EP1990/000629 patent/WO1990013545A1/en not_active Application Discontinuation
- 1990-04-19 CA CA 2053876 patent/CA2053876A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6031031A (en) * | 1997-09-10 | 2000-02-29 | Basf Aktiengesellschaft | Thermoplastic molding compositions based on polyesters and polycarbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3914159A1 (en) | 1990-10-31 |
| EP0394854A1 (en) | 1990-10-31 |
| JPH04504853A (en) | 1992-08-27 |
| BR9007324A (en) | 1992-04-28 |
| WO1990013545A1 (en) | 1990-11-15 |
| EP0470107A1 (en) | 1992-02-12 |
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