DE1035641B - Process for the production of polyacetoxy fatty acid esters - Google Patents

Description

ÖEÜTSCHES

The invention relates to a process for the preparation of polyacetoxy fatty acid esters which contain one or contain multiple pairs of acetoxy groups attached to adjacent carbon atoms of the original double bonds are bound either in the alcohol or in the acid residue of the ester or in both, from double bonds containing fatty acid esters. In particular, these are diacetoxy or poly (diacetoxy) derivatives of esters of unsaturated vegetable fatty acids and diacetoxy or poly (diacetoxy) derivatives of esters of unsaturated long-chain alcohols.

The products of the process of the invention are excellent as plasticizers for plastics in general, but especially suitable for polyvinyl resins.

The method of the invention is that first an unsaturated ester with a mixture of hydrogen peroxide, acetic acid and / or acetic anhydride and an additional acidic auxiliary in certain proportions explained in more detail below is treated in the aqueous phase, with oxy and acetoxy groups at the points of the double bonds as well as some epoxy groups are introduced; then the organic phase is separated from the aqueous phase and treated with acetic anhydride or with ketene and acetic acid, thereby forming the oxy and epoxy groups be converted into acetoxy groups.

The process is distinguished from known methods (U.S. Patents 2,660,563 and 2,073 Oil) in that there are both quick and operational methods of manufacture of polyacetoxy fatty acid esters

Applicant:

Rohm & Haas Company, Philadelphia, Pa. (V. St. A.)

Representative: Dr.-Ing. Dr. jur. H. Mediger, patent attorney, Munich 9, Aggensteinstr. 13th

Claimed priority: V. St. v. America August 30, 1954

Arthur William Ritter Jr., Haddon Heights, N.J.,

and Stanley Paul Rowland, Philadelphia, Pa. (V. St. A.),

have been named as inventors

Dodecyl linolenate. However, mixed esters of the acids are also suitable for the process.

Semi-drying and drying vegetable oils are

works safely, to practically completely saturated end products. 30 Examples of naturally occurring mixed glycerine products and also a hydrolysis of the ester- esters of oleic acid, linoleic acid and linolenic acid, which are

can be used excellently. The semi-drying oils are essentially mixed esters of glycerine with oleic acid, linoleic acid and saturated monocarboxylic acids, ΐηε-special Stearic acid. When treated according to the present process, the acetoxy groups occur to the double bonds without the presence of the ester of the saturated fatty acids affecting the course of the reaction somehow noticeably influenced.

In addition to oleic and linoleic acid, drying oils also contain tri-unsaturated linolenic acid. These too According to the process, oils can be made to react. Herbal ingredients that are particularly suitable for the process Oils are the oils from soybean, corn, to name a few. Tree-

Butyl, n-octyl, 2-ethylhexyl, octadecyl, lauryl, 45 wool seeds, safflower, sunflower, sesame, poppy seeds, whale cyclohexyl and Benzyl alcohol; polyhydric alcohols, nut, peanut, flaxseed and perilla.

The average degree of unsaturation of the esters, the amounts of peroxide to be used and

bindings of the parent ester does not take place. The end products are therefore extremely well tolerated with polyvinyl resins and other plastics that are difficult to leak out of.

The process of the invention is applicable to the esters of water-insoluble unsaturated fatty acids and is particularly suitable for processing the higher molecular weight found in natural vegetable oils unsaturated fatty acids, the most important of which are oleic acids, linoleic acid and linolenic acid. It their esters with mono- or polyhydric alcohols, eg. B. mono-, di- and trisubstituted carbinols, such as ethyl, isopropyl, η-butyl, sec-butyl, tert.

such as ethylene glycol, i, 2-propylene glycol, 2-EthyIhexanediol-1,3, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,

Dodecanediol-1,12; Polyalkylene glycols, such as di- and acetic acid and / or acetic anhydride,

Triethylene glycol, glycerin; Pentaerythritol, its iso-50, is either known or can easily be traced back to known

mers and homologues of the named.

Likewise, esters of alcohol mixtures, e.g. B. ethyl oleate - butyl oleate or benzyl linoleate - cyclohexyl linoleate, Octyl oleate — dodecyl linoleate, octyl linolenate— Determine methods (e.g. by determining the bromine or iodine number).

The esters of substituted alcohols, such as the esters of polyalkylene glycols, especially polyethylene

ai »5βΟ / 570

3 4

glycols that contain only inert substituents that are not included in the process between 0.3 and 2.5 moles each

react with the aqueous peroxide mixture can double bond per mole of unsaturated ester with the

also reacted by the process, provided that the amount of acetic acid or anhydride

will. The same applies to esters of aromatic alcohols, inversely proportional to the concentration of the aqueous

like benzyl alcohol. However, preferred are suitable for the 5 H ₂ O ₂ solution within points A, B, C, D des

Method ester unsubstituted saturated alipha diagram is to be selected.

table alcohols, namely those of alcohols, alkane At least 1 mole of H ₂ O ₂ is for each double bond each

diols, alkane triols and alkane tetrols. Moles of ester required. So there is at least 1 mole of H ₂ O ₂

The method of the invention is also applicable to esters of others, such as an oleic acid ester of a monovalent one

unsaturated acids as oleic, linoleic and linolenic acid ¹⁰ alcohol or an oleyl ester of a saturated lower one

applicable, e.g. B. to convert the ester of undecylenic acid, palmito fatty acid into an acetoxy derivative. A

Oleic acid, petroselic acid, erucic acid, myristolenic acid. Esters with two double bonds, such as hexyl linoleate or

The same applies to the esters, the unlinoleyl butyrate in the alcohol residue requires 2 moles of H ₂ O ₂ .

are saturated. Since the reaction products predominantly as usual, an excess of H ₂ O _{2 is} used,

Plasticizers used for plastics have 15, generally 0.1 moles over the

Esters of long chain alcohols, e.g. B. the theoretically required 1 mole with oleyl, linoleyl is appropriate. Man

and linolenyl alcohols are of greatest interest. However, this can be up to a whole mole excess, i. H. into the-

Esters are available in pure form, but the total of 2 moles of H ₂ O ₂ per mole of double bond can also be used. At-

The usual types are sufficient. The esters of the so-called applicable are all commercially available aqueous peroxide

th oil alcohols are also suitable for the process. 2 ° solutions with 35 to 90% H ₂ O ₂ content are preferable

They are made by reducing esters of mixed fats _{- those with at least 50% H 2} O ₂ content. The Concentrated

Acids of vegetable oils, such as the oils of soy, linseed, trier solutions are kept at a low temperature

Safflower, cottonseed and perilla, using sodium and and / or using a lower mol

an alcohol such as ethanol or butanol. Ratio of acetic acid or anhydride applied,

The 25 obtained by the present process inversely the more dilute solutions.

Acyloxy ester mixtures are also excellently suited.

as stabilizers and plasticizers. mix of hydrogen oxide and acetic acid and resp.

Similarly, the method is applicable to the esters of acetic anhydride or have a p _H of +1.5 to said unsaturated fatty acids with said -1,5 because they will always be added to an acidic adjuvant, unsaturated alcohols such. B. Oleyl oleate, oleyl linoleate. As such, oleate, oleyl linolenate, linoleyl linolenate, linoleyl linoleate, for example, can be used with excellent success: inorganic acids such as phosphoric acid, linolenyl oleate, linolenyl linoleate, linolenyl linolenate. That- sulfuric acid, hydrochloric acid, nitric acid, boron acid applies to the esters of oleic alcohols and vegetable acids; acidic salts, such as sodium or potassium fatty acids, such as the esters of soy alcohols and soy bisulphate, potassium persulphate, zinc chloride; organic sulfonic fatty acids. 35 acids such as toluenesulfonic acid, methanesulfonic acid; strength

In the first stage of the process it is important that carboxylic acids such as molic acid, fumaric acid, oxalic acid; the reactants in the aqueous phase in acidic esters such as monoethyl phosphate, monoisopropyl proportions to one another are such that a bisphosphate, mono- and dimeth sulfate.
The acidic auxiliary must form acetoxy groups in the aqueous medium and a minimum of epoxy ions, so that this has the required p _H groups. It is also important that the acidic auxiliary should react as quickly as possible in order to avoid low solubility in the ester to be treated due to hydrolysis of the ester or degradation and damage. Inorganic auxiliaries are therefore cheaper to avoid coloring the end product. than organic ones, which generally have a greater

In the process, peracetic acid in situ will tend to be in the organic phase and, like aqueous maleic acid Formed intimately with the water-insoluble acid or oxalic acid, to reactions such as formation of the phase borrowed starting ester is mixed. corresponding esters, which tend to be in terms of the

Either acetic acid or acetic anhy- Purpose of the present process are undesirable

apply drid or their mixture. As part of the By numerous proven acid relief agencies have

In the process, 1 mole of anhydride is equivalent to 2 moles of acetic acid - 5 ° sulfuric acid and especially phosphoric acid

lent. Proven to be most suitable for the reaction sequence described above.

deliver, the amount of acetic acid and / or by the presence of the acidic auxiliary must run

Acetic anhydride on the concentration of each other- the reaction smoother and faster,

applied aqueous H ₂ O ₂ solution, * The reaction can take place at a temperature up to

and it must be inversely proportional to this. 55 can be carried out below 10 ° C, but in the gfößtech-

The drawing shows a diagram in which the required niche scale is expediently between 70 ° C Hnd

Amounts of acetic acid in moles worked against the concentrations of the boiling point of the reaction mixture,

aqueous hydrogen peroxide solutions are applied. Hydrogen peroxide and acetic acid are preferred

The dashed area between points A, B ₁ C, D and / or or anhydride and the acidic auxiliary agent dem

is a measure for the measurement of the appropriate 60 esters at the same time uftd individually in the corresponding

Amount of acetic acid and / or acetic anhydride added in amounts within such times that the

any given concentration of the H ₂ O ₂ solution. So temperature can be kept within the desired limits

must z. B. when using a 35% aqueous can. But it is also possible for the reaction participants

H ₂ O ₂ solution, add the amount of acetic acid and / or its batchwise in such an amount that the p _H value

Anhydride 0.7 to 2.5 mol per double bond per mol of the aqueous phase within the limits +1.5 to -1.5

unsaturated ester, if one is used. Especially when processing tons of

90% aqueous H ₂ O ₂ solution, on the other hand, 0.3 to 1.0 mol of ester, it has proven useful to put the reactants in

per double bond. Between these limits there are roughly nine equal parts at intervals of 30 minutes

to interpolate speaking. Accordingly, admitting moves. It is not advisable to use hydrogen peroxide and

the total amount of acetic acid and / or anhydride 70 acetic acid and / or anhydride must be mixed beforehand,

as this is dangerous. In the process, peracetic acid should be formed and converted "in situ".

After the first stage, the reaction mixture is separated into an aqueous and an organic phase. this can be accelerated very much by adding a water-immiscible liquid which dissolves the ester. An organic solvent such as toluene or ethylene dichloride is suitable. The ester is then heated to Water and any solvent used to ent

Example 2

a) In the device of Example 1, a) a solution of 366 g (1.0 mol) of 2-ethylbutyl oleate in 366 g of toluene is stirred vigorously and at 70 to 75 ° C with ten portions of 5.6 g of a 70 ° / ₀ by weight H ₂ O ₂ solution (1.15 mole total), 0.374 g of 85% phosphoric acid (total 0.03 mol) and 6.35 g of acetic anhydride (total 0.622 mole) was added, the added quarter-hour will. The mixture is stirred at 70 to 75.degree

distant, and in the second process stage with acetic acid for a further hour and then isolated as above the acid anhydride or with a mixture of acetic acid 2-ethyl-butyloxyacetoxystearate in an amount of and ketene to the reaction. Acetic anhydride
is preferable for this acetylation. In general

acetic anhydride or acetic acid ketene

393 g. Iodine number = 1; Hydroxyl number = 140; 0.13% epoxy oxygen. Yield: 393 g.

b) 100 g (0.226 moles) of this ester are at about

mix in excess, to the reaction with the OH 15 135 ° C under reflux with 45.5 g (0.446 mol) of acetic acid groups and any epoxy groups treated with stoichiometric anhydride and 0.3 g of sodium acetate. Then will

volatile components distilled off at 100 ° C / 30 mm and that 2-ethyl butyl diacetoxystearate obtained is filtered; Epoxy

required amount, applied. Methods for determining the hydroxyl numbers and the epoxy oxygen content are known. An excess of more than 400% of the acetylating agent is useless. In every 20 loot: In this case, the excess can be recovered and reused. Small amounts of a neutral or weak basic salt, such as sodium acetate, have a catalyzing effect on acetylation, and such an addition is therefore to be avoided

oxygen = 0, hydroxyl number = 0, iodine number = 1.0. Off-115 g.

Example 3

a) The procedure of Example 2 is recommended on soy. Amounts of about 0.1 to about 2 _{°; o} sawn applied 25 bean oil. A solution of 188 g (1 mol based on the ester weight, are appropriate here. Double bond) of the oil in 188 g of toluene is stirred at 70 to 85 ° C, while 88, 5 g of 50% H ₂ O ₂ solution, boiling point of the reaction mixture, and the (1.3 mol of H ₂ O ₂ ), 0.74 g of 85% phosphoric acid and 40.8 g of acetylation is complete in at least one hour. (0.4 mol) acetic anhydride in ten portions in single-Then the ester / on volatile impurities is added at intervals of 15 minutes. The intermediate and excess reactants by Er- (polyacetoxy-oxysoybean oil) contains 2% epoxy acid heat exempt. This is expediently done with the reagent and has an iodine number of 2. Yield: 203 g.

b) 100 g of the intermediate product are mixed with 200 g of acetic anhydride containing 2.5 g of sodium acetate 135 ° C acetylated. The poly (diacetoxy) glyceryl ester obtained in this way (yield 111 g) has an iodine number of 2, epoxy oxygen and hydroxyl number = 0. Although its viscosity is 148 poises, the acetoxylated oil is

is compatible with polyvinyl chloride and has an i

Example 4

tion temperature. Then the end product is nitrided and is ready for use.

All process products are made with polyvinyl chloride, 35
with polyvinyl acetate and their mixture merisates, with
Copolymers of polyvinyl chloride and polyvinylidene chloride compatible. They are also in
such masses are more stable than the intermediates obtained in the first process stage, which have both a hydroxylic plasticizer effect,
contain as acetoxy and epoxy groups.

The following examples explain the process of the invention in more detail.

a) A solution of 338 g of butyl oleate (1 mol) in 338 g of benzene is introduced into a reaction vessel of the type described in Example 1. A total of 1.15 mol of H ₂ O ₂ as a 70% strength aqueous solution, 0.622 mol of acetic anhydride and 0.0324 mol of phosphoric acid are added individually and simultaneously in the same proportions. to 70 ° C., stir and add 88.4 g of 50 over the course of 4 hours. The reaction takes 7 ¹ J ₁ hours at 65 to 72 ° C. The butyl acetoxystearate isolated from a 50% strength aqueous hydrogen peroxide solution according to Example 1, a) has the (1.3 mol H ₂ O ₂ ), 102 g (1 mol) acetic anhydride and iodine number 1 and 0.13% epoxy oxygen content. From-5.76 g (0.05 mole) of 85% phosphoric acid. You stir the booty: 347 g.

at 70 ° C for a further Z ¹ J ₂ hours and then diluted with b) 188 g of this product are as in Example 1, b)

300 ecm of water. The organic phase is acetylated with water. The end product (butyl 9,10-diacetoxystearate washed and heated to 100 ° C./1 mm. The reaction is practically identical to that of Example 1. Yield: ition product (butyloxyacetoxystearate) has an iodine number = 2.0, only 0 , 26% epoxy oxygen, acid number = 2.5,
Hydroxyl number = 178. Yield: 352 g.

b) 188 g (0.455 mol) of the product obtained according to a) are stirred at 130 to 136 ° C for 4 hours in

example 1

a) A solution of 338 g (1 mol) of butyl oleate in 338 g of benzene is poured into a stirrer, thermometer and reflux condenser provided vessel entered. One warms up

203 g.

Example 5

a vessel equipped with a stirrer, thermometer and reflux condenser with 91 g (0.89 mol) of acetic anhydride, containing 0.6 g of Na acetate, acetylated. Acetic acid and acetic anhydride are then used at 125 to 135 ° C / 1 mm distilled off. The filtered butyl 9,10-diacetoxystearate has the iodine number 1.8, acid number = 3.0, 0% epoxy oxygen, hydroxyl number = 0. It is with polyvinyl chloride dispensed compatible and stable. Yield: 205 g.

a) The procedure is as in Example 2, a), but instead of 0.622 mol of acetic anhydride, 1.24 mol of acetic acid is used. 2-Ethylbutyloxystearate with 0.9% epoxy oxygen content is obtained. Yield: 350 g.

b) 100 g of this product are mixed with 45.5 g of acetic anhydride and 0.3 g of sodium acetate for 4 hours at about 135 ° C acetylated, then the volatile is distilled off at 100 ° C / 1 mm and the cooled residue is nitrated. That 2-ethylbutyl diacetoxystearate has an iodine number of 1.0 and an epoxy oxygen content = 0.26%, hydroxyl number = O. Yield: 114 g.

Claims (5)

I. Example 6 .. a) As in example 2, a). 115 g of cotton seed oil (0.5 mol of double bonds) in 115 g of toluene,,. 75 ° C. Man. Bej is 65 to 75 ° C in half-hour intervals ten portions each of 4.5 g of 5O ° / _O strength H ₂ O ₂ solution (total .0,65 _moles): 0.3 g of 85 ° / _o phosphoric acid (0.26 mol in total) and 5.1 g of acetic anhydride (0.5 mol in total) are added, the mixture is stirred for a further 4 hours at about 70 ° C., washed and heated in vacuo. The polyacetoxy cottonseed oil obtained contains practically no epoxy oxygen. Yield: 125 g. b) The oil is acetylated with 102 g (1 mol) of acetic anhydride for 3 hours at 135 ° C. and freed from vpn under reduced pressure. Acetic acid and anhydride. A polydiacetoxy cottonseed oil is obtained with a viscosity of over 300 poises, epoxy oxygen = 0, hydroxyl number = 0, the _; is extremely compatible with polyvinyl chloride with a considerable plasticizer effect. Yield: 124 g. Example 7 a) The procedure is as in Example 1 with oleyl butyrate instead of butyl oleate. The intermediate product (352 g Stearyloxyacetoxybutyrat) has only 0.3 ° / ₀ epoxy oxygen and the iodine value 1.6 ... b) The acetylation leads to 205 g. Stearyl diacetoxybutyrate without epoxy oxygen content with an iodine number of 1.4 and a hydroxyl number of 0. Example 8 Butyloxyacetoxystearate, prepared according to Example 1, a), is dissolved in 120 g of acetic acid and 84 g of ketene is allowed to enter the reaction mixture at such a rate occur that no gas escapes. The mixture is then in a with stirrer, thermometer and reflux condenser equipped vessel heated to 130 to 136 ° C with stirring and held at this temperature for 4 hours. After removal of the volatile constituents, it is then distilled under 1 mm pressure at 125 bis 135 ° C. and, after filtration, receives 200 g of butyl 9,10- (diacet) oxystearate. Analysis data as in example 1, b). The product is a very good plasticizer for polyvinyl chloride. Contain acetoxy groups, characterized in that in a first stage at a temperature between about 10 ° C and the boiling point of the reaction mixture, water-insoluble olefinically unsaturated fatty acid esters are treated with an aqueous mixture containing hydrogen peroxide, acetic acid and / or acetic anhydride and also an ionizable acidic auxiliary , and having a p _H of + 1.5 to - has 1,5, wherein the amount of hydrogen peroxide per 1 mole of double bond is at least 1 mol and the amount of acetic acid or anhydride inversely proportional to the selected Wasserstoffperoxydkonzentration within the through points (a , B, C and D) is the limited area of the diagram, then the ester mixture separated from the aqueous mixture, which contains not only acetoxy but also oxy and epoxy groups, in a second stage practically with exclusion of water at a temperature of about 100 ° C to the boiling point of the reaction mixture, with acetic anhydride or a Gemi sch from ketene and acetic acid, advantageously in the presence of sodium acetate or another neutral or weakly basic salt acetylated until the hydroxyl number and the epoxy oxygen content have reached practically zero, whereupon the acetoxy ester is isolated from the reaction mixture in a known manner. 2. The method according to claim 1, characterized in that the starting ester in one organic solvent dissolves. 3. The method according to claim 1 and 2, characterized in that the starting ester is a vegetable Oil used. 4. The method according to claim 1 to 3, characterized in that one alkyl esters of oleic acid, linoleic acid or linolenic acid. 5. The method according to claim 1 to 4, characterized in that the acidic auxiliary in the first stage of the process, a strong mineral acid, in particular phosphoric acid, is used. PATENTANSI'K TLC: 1. Process for the preparation of polyacetoxy fatty acid esters, at least one pair of adjacent Publications considered: Markley, "Fatty acids" (New York 1947), pp. 422 bis 424; Journal of the American Chemical Society, 67 (1945), 1786-1789. 1 sheet of drawings © 809 580/570 7. 5 »