Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/40—Succinic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
  • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/60—Maleic acid esters; Fumaric acid esters

Definitions

• the invention relates to compounds containing ester groups with at least three ester functions, processes for their preparation and the use of the products.
• Monoesters of dicarboxylic acids are known. Attempting to condense these compounds with di- or polyols leads to the formation of polycondensates and it is not possible to obtain low molecular weight compounds in a technically usable reaction.
• GB-PS 1,379,335 describes the attempt to prepare emulsion stabilizers by reacting unsaturated glycidyl esters with dicarboxylic acid monoesters. Because of the tendency to rearrange the resulting products and their sensitivity to temperature, the lengthy implementation leads to polymer-containing or unstable end products which do not allow economical industrial use.
• the present invention is based on the object, starting from dicarboxylic acid monoesters, of providing stable compounds containing a plurality of ester functions and a process for their preparation.
• Y bivalent, saturated aliphatic hydrocarbon radical which may be substituted with one or more etherified or esterified hydroxy groups
• Z acyl radical -CO-R of a mono- or dibasic, saturated or unsaturated aliphatic, cycloaliphatic or aromatic carboxylic acid with 2 to 22 C atoms, which optionally carries a saturated or unsaturated C4 ⁇ Ci5 hydrocarbon radical as a substituent,
• the first synthetic route comprises the reaction of a dicarboxylic acid monoester with an epoxide, ie an alkoxylation of the Carboxylic acid group, the intermediate dicarboxylic acid monoester alkoxylate (dicarboxylic acid hydroxyalkyl alkyl diester) which is thermally unstable, then acylated and thereby converted into the form of the stable triester.
• the resulting dicarboxylic acid monoester alkoxylates have the general formula:
• the acylation of the hydroxyalkyl group of the intermediate product which tends to condense further, leads to the formation of the temperature-stable triesters. It is carried out at temperatures between 50 and 120 ° C, preferably 60 to 90 ° C and is applicable to practically all hydroxyalkyl-alkyl dicarboxylic acid mixed esters.
• a residual amount of unreacted dicarboxylic acid monoester in the reaction mixture after alkoxylation has a stabilizing effect on the hydroxyalkyl-alkyl mixed ester formed.
• the acid number of the alkoxy mixture is preferably at least 5; at values below 5, considerable pressure fluctuations and rearrangement reactions occur.
• the acid number is preferably at least 10.
• hydroxyalkyl-alkyl-dicarboxylic acid esters produced in this way have a lower melting point and less water solubility than the dicarboxylic acid monoester, especially in the neutral to weakly alkaline range. This often enables the hydroxyalkyl ester to be cleaned with water or an aqueous salt solution.
• the intermediate product is therefore preferably further processed immediately.
• the dicarboxylic acids used to produce the starting dicarboxylic acid monoesters can be aliphatic, saturated or unsaturated acids. Essential representatives of the dicarboxylic acids are succinic, maleic, fumaric acid.
• Anhydride-forming acids are preferred since the monoesters are most easily prepared from the anhydrides of dicarboxylic acid.
• Any mono- or polyvalent saturated or unsaturated primary, secondary or tertiary alcohols can be used as the alcohol component for forming the dicarboxylic acid monoester.
• alkylene oxide adducts containing acidic hydrogen can also be used.
• the degree of conversion of the ester formation can be followed in the usual way via an acid or OH number determination.
• the quantitative ratios between alcohol and dicarboxylic acid or anhydride are chosen according to the stoichiometric conversion to the half ester. Partial esterifications are also possible with polyhydric alcohols.
• the reaction is conducted at temperatures below 120 C C, preferably below 90 leads ⁇ Vietnamesege C, but can also, if the melting point of Anhy ⁇ is drids higher, are briefly höht er ⁇ up to this temperature.
• work is carried out in the pressure vessel.
• the monoesters produced are expediently further processed directly while they are still hot because of their thermal instability.
• All compounds with an epoxy structure can be used to form the hydroxyalkyl esters.
• the following are mentioned as preferred representatives of the group of epoxides: ethylene oxide, propylene oxide, 1,2-epoxy butane, 2,3-epoxy l-propanol, glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, 1,3-butanediene monoxide, styrene oxide, Epoxy butyric acid ethyl ester, 1,2-epoxy cyclodeca-5,9-diene, 1,2-epoxy cyclododecane, 1,2-epoxy cyclohexane, exo-2,3-epoxinorbornane, 2,3-epoxy propyl 4-methoxy phenyl ether, N- (2,3-epoxypropyl) phthalimide.
• a sterically and / or kinetically unfavorable choice of the reactants can lead to an impairment of the reaction times and / or yields.
• the thermally stable triesters are obtained by reacting the thermally unstable intermediate with an acylating agent.
• Carboxylic acid anhydrides, carboxylic acid chlorides or ketenes are preferably used for the acylation.
• the acylation is carried out following the epoxy addition to the dicarboxylic acid monoester at the same Chen temperature carried out.
• Transesterification or polymer formation are prevented by the acylation of the OH groups.
• the type and length of the hydrocarbon residue in the acylating agent have a greater influence on the physical properties of the mixed ester than that of the alcohol residue of the dicarboxylic acid monoester.
• the acetyl-oxyethyl-benzylmaleinate is a low-viscosity, clear liquid at room temperature, while the benzoyl-oxyethyl-methylmaleinate is rearranged under the conditions of distillation to form the fumaric acid ester and forms a white crystals below 51 ° C.
• the hydroxyalkyl alkyl esters are reacted with dicarboxylic anhydrides in a manner similar to the formation of the monoesters described above.
• the Triester molecule obtained has both the structure of a dicarboxylic acid diester and that of a dicarboxylic acid monoester. Both the same and different basic dicarboxylic acids can be combined in one molecule.
• the carboxylic acid anhydrides are selected according to the same criteria as described for the production of dicarboxylic acid monoesters.
• a direct possibility for the synthesis of the triesters is the reaction of dicarboxylic acid monoesters with alkylene carbonates, such as, for example, ethylene (1,3-dioxolan-2-one) or propylene carbonate (4- methyl-1,3-dioxolan-2-one) simultaneous presence of an acylating agent.
• alkylene carbonates such as, for example, ethylene (1,3-dioxolan-2-one) or propylene carbonate (4- methyl-1,3-dioxolan-2-one) simultaneous presence of an acylating agent.
• the stage of the thermally unstable intermediate, the hydroxyalkyl alkyl dicarboxylic acid diester is skipped.
• the possible higher reaction temperatures of above 120 ° C enable higher reaction rates on the one hand and on the other hand when using low-boiling anhydrides as acylating agents, e.g. Acetic anhydride, the direct distillation of the released monocarboxylic acid.
• This process is particularly suitable for the production of small amounts of triester and for the implementation of dicarboxylic acid monoesters with a high melting point, in which a hydroxyalkylation with an epoxy would lead to rearrangements and polyester formation.
• thermally stable and storage-stable triesters according to the invention have advantageous properties with regard to consistency, smell, boiling point, flash point combined with an adjustable oil or water compatibility.
• the presence of the at least three functional ester groups and the possibility of varying at least three structural elements of the triester according to the invention results in a large number of possible compounds according to the teaching of the invention which are of interest as solvents or solubilizers, plasticizers, antistatic agents and lubricants .
• the sulfited triesters of unsaturated carboxylic acid have wetting properties.
• the products are generally readily biodegradable and thus have a high level of environmental compatibility.
• unsaturated groups e.g. Esterification with an unsaturated alcohol, e.g. Allyl alcohol with a dicarboxylic acid or by acylation with an unsaturated carboxylic acid, e.g. Acrylic acid
• polymer components are formed which can bring out the advantages listed, for example, as permanent plasticizers in polymerized form in a polymer body.
• the thermal stability of the triesters according to the invention is so high that vacuum distillation is possible even at high temperatures without decomposition, so that the triester obtained can be purified by means of a fractionation column.
• unsaturated triesters e.g. the maleates
• isomers e.g. the fumarates
• the identification and characterization of the liquid triesters distilled under high vacuum can be by determining density d, refractive index n and molar mass M.
• Table 1 gives an overview of the raw materials used and the boiling points of the triesters obtained as well as the densities and refractive indices at 20 ° C. Above the boiling temperatures listed (approx. 20 to 30 ° C. higher), further fractions are obtained which result from multiple attachment of the epoxide to the dicarboxylic acid monoester.
• esters according to the invention were produced: 11
• MSA maleic anhydride
• BSA succinic anhydride
• EO ethylene oxide
• PO propylene oxide
• EC ethylene carbonate
• AcA acetic anhydride
• stear. Stearic acid chloride
• PEG 600 polyethylene glycol of molecular weight 600.
• Acetyl-oxiethyl-methylmaleinate 780 g of monomethyl maleate, prepared from 588 g of maleic anhydride and 192 g of methanol at 70 ° C., were heated to 80 ° C. in an autoclave under nitrogen with 396 g of ethylene oxide in the presence of 10 g of dimethylbenzylamine. After a reaction time of 1 hour, the acid number had dropped to 16 (0.28 mmol / g). 700 g of acetic anhydride were added to the reaction product and the mixture was then stirred at 80 ° C. for a further 1 hour. The contents of the reaction vessel were then distilled over a fractionation column under high vacuum.
• the product passed at 102 ° C (0.1 mbar) and was an odorless, low-viscosity liquid with a density of 1.19 g / ml and a refractive index of 1.455 at 20 ° C. 13
• Acety1-oxipropyl-methylmaleinate Analogously to Example 1, 780 g of monomethyl maleate were reacted with 504 g of 1,2-epoxypropane in the presence of 10 g of dimethylbenzylamine and then with 700 g of acetic anhydride. The reaction mixture was then subjected to fractionation.
• the product had a boiling point of 105 ° C (0.1 mbar) and a density of 1.16 g / ml and a refractive index of 1.453 at 20 ° C.
• Acetyl-oxiethyl-ethyl maleate 864 g of maleic acid monoethyl ester, prepared from 588 g of maleic anhydride and 276 g of ethanol at 70 ° C., were heated to 39 ° g in the presence of 10 g of dimethylbenzylamine at 80 ° C. in an autoclave under nitrogen. After a reaction time of 1 hour. 700 g of acetic anhydride were added and then strig ⁇ times 1 hr. At 80 C ⁇ stirred.
• a second fraction was obtained at 125 to 130 ° C and consisted of the acetylated diethylene glycol and triethylene glycol ester of monoethyl maleate.
• Acetyl-oxiethyl-2-ethylhexyl maleate 1824 g of mono-2-ethylhexyl maleic acid, prepared from 784 g of maleic anhydride and 1040 g of 2-ethylhexanol, with 528 g of ethylene oxide in the presence of 20 g of dimethylbenzylamine and then ⁇ d with 900 g of acetic anhydride at 80 C C.
• a second fraction was obtained between 135 and 138 ° C and consisted of the acetylated diethylene and triethylene glycol ester of monomethyl maleate.
• Acetyl oxyethyl benzyl maleate 824 g of maleic acid monobenzyl ester, prepared from 392 g of maleic anhydride and 432 g of benzyl alcohol, were reacted with 264 g of ethylene oxide in the presence of 10 g of dimethylbenzylamine and then with 450 g of acetic anhydride at 80 ° C. After acylation 15
• the triester was distilled under vacuum over a fractionating column.
• the compound had a boiling point of 148 ° C. at 0.1 mbar. At 20 ° C. it had a density of 1.19 g / ml and a refractive index of 1.511. It was an odorless, low-viscosity, water-clear liquid.
• the distillate removed above 160 ° C. mainly contained the acetylated diethylene glycol and triethylene glycol esters of monobenzyl maleate / fumarate.
• Acetyl oxyethyl methyl succinate 792 g of methyl succinate, prepared from 600 g of succinic anhydride and 192 g of methanol, were reacted with 396 g of ethylene oxide in the presence of 10 g of dimethylbenzylamine and then with 700 g of acetic anhydride at 80 ° C. After the acylation, the reaction mixture was distilled under high vacuum.
• the compound was obtained at 102 ° C. (0.1 mbar) and at 20 ° C. was an odorless, low-viscosity, water-clear liquid with a density of 1.17 g / ml and a refractive index of 1.439.
• a second fraction was obtained at 125 to 130 ° C., which consisted of the acetylated diethylene glycol and triethylene glycol esters of the monomethyl succinate.
• Acetyl oxiethyl ethyl succinate 876 g of succinic acid monoethyl ester, made from 600 g of succinic anhydride and 276 g of ethanol were reacted at 80 ° C. with 396 g of ethylene oxide under nitrogen in an autoclave in the presence of 10 g of dimethylbenzylamine and then with 700 g of acetic anhydride at the same temperature. After the acetylation, the reaction mixture was distilled under high vacuum.
• the compound had a boiling point of 103 ° C at 0.1 mbar and placed at 20 C C an odorless, low-viscosity, ement ⁇ clear liquid having a density of 1.13 g / ml and a refractive index of 1.441 is.
• Acetyl-oxiethyl-n-propyl succinate 160 g of succinic acid mono-n-propyl ester, prepared from 100 g of succinic anhydride and 60 g of n-propanol, were heated to boiling with 90 g of ethylene carbonate and 140 g of acetic anhydride with a connected fractionating column. From 140 ° C the mixture reacted to form acetic acid, which was taken off at the top of the column. The temperature was slowly raised to 200 ° C and left there for 1 hour. The mixture was then cooled to about 50 ° C. and the vacuum distillation started.
• the compound had a boiling point of 103 to 104 ° C at 0.1 mbar and at 20 ° C was an odorless, water-clear, low-viscosity liquid with a density of 1.11 g / ml and a refractive index of 1.440.
• Stearoyl-oxiethyl-methyl fumarate 390 g of maleic acid monomethyl ester (see Example 1) were reacted at 80 ° C. with 198 g of ethylene oxide in the presence of 5 g of dimethylbenzylamine in an autoclave under nitrogen and then with 910 g of stearic acid chloride at the same temperature treated.
• the reaction product was distilled under high vacuum, the compound passing over at 220 ° C. (0.3 mbar) and being kept above its melting point in the cooling device. After recrystallization in acetone, the compound had a melting point of 61 ° C. The appearance and consistency of the substance resembled a hard wax.
• Benzoyl-oxiethyl-methyl fumarate 780 g of monomethyl maleate (see Example 1) were reacted with 396 g of ethylene oxide in the presence of 10 g of dimethylbenzylamine at 80 ° C. in an autoclave under nitrogen and then at 845 for 1 hour at the same temperature g treated with benzoyl chloride. Thereafter, the triester was distilled under a high vacuum using a fractionation column and kept above its melting point in the cooling receiver.
• Example 12 The compound had a boiling point of 147 ⁇ C at 0.25 mbar. After recrystallization from acetone, white needles with a melting point of 51 ° C. were obtained.
• Example 12
• Bis-acetoxiethylmaleinklain yarn-diethylene glycol 1224 g of bis-maleic acid-diethylene glycol monoester, prepared from 636 g of diethylene glycol and 588 g of maleic anhydride at 70 ⁇ C were reacted with 396 g ethylene oxide in the presence of 10 g of dimethylbenzylamine in an autoclave under nitrogen at 80 ° C, and then acylated with 700 g of acetic anhydride. The reaction mixture was then poured into about 2 l of cold water, shaken vigorously and the aqueous phase was discarded. A saponification number of 547 was determined for the water-insoluble triester.
• Bis-acetoxiethyl-maleic acid-polyethylene glycol (600) -ester 1592 g bis-maleic acid-polyethylene glycol (600) -monoester, made from 1200 g of polyethylene glycol (OH number: 187) and 392 g of maleic anhydride, were mixed with 198 g of ethylene oxide in the presence of 10 g of dimethylbenzylamine in an autoclave under nitrogen at 80 ° C and then acylated with 600 g of acetic anhydride. Thereafter, the research was endeavorsmi ⁇ in about 2 1 of warm water (about 60 C ⁇ ) was poured and shaken vigorously. After settling, the aqueous phase was discarded and the remaining oil was dried.
• the polyglycol ester had a saponification number of 331 and a cloud point of approx. 53 ° C.
• n-octenyl-succinoyl-oxy-ethyl-octadecyl maleate 1083 g of n-oc-tadecyl maleate, produced from 789 g of Alfol 16/20 (trade name from Condea, FRG, for a fatty alcohol c 16-2 ⁇ ) and 294 g of maleic anhydride, were with 145 g Ethylene oxide in the presence of 10 g of dimethylbenzylamine reacted at 80 ° C. in an autoclave under nitrogen and then aftertreated with 630 g of n-octenyl succinic anhydride for 1 hour at the same temperature.
• reaction product was then shaken vigorously with water (about 50 ° C.), separated off and dried.
• the result was a light yellow oil with an ester number of 4.99 mmol / g and an acid number of 85.
• a water-soluble gel spontaneously formed with alkali or ammonia.
• Isododecenyl succinoyl oxiethyl octadecyl maleate As described in Example 12, 1228 g of oxyethylated octadecyl maleate were reacted with 795 g of isododecenyl succinic anhydride. After cleaning with warm water and drying, a yellow oil with an ester number of 4.30 mmol / g and an acid number of 78 was obtained. When alkali or ammonia was added, the product was water-soluble to form a gel.
• Acetyl oxyethyl allyl maleate 936 g of maleic acid monoallyl ester, prepared from 588 g of maleic anhydride and 348 g of allyl alcohol, were reacted with 396 g of ethylene oxide in the presence of 10 g of dimethylbenzylamine and then with 750 g of acetic anhydride. The reaction mixture was then subjected to fractionation under vacuum. 500 ppm of phenothiazole were used for stabilization.
• the compound had a boiling point of 106 ° C. at 0.15 mbar and had a density of 1.16 g / ml or a refractive index of 1.465 at 20 ° C. It was water-clear, fluid and almost odorless. 20th
• a second fraction was obtained between 120 and 130 ° C. This was the acylated diethylene glycol and triethylene glycol ester of monoallyl maleate.

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