DE2942599C2 - Catalytic process for the disproportionation of rosin and / or polyunsaturated fatty acids - Google Patents

Description

0.01 to 5 wt .-% iron, iron oxide, iron hydroxide and / or iron sulfide, each based on the starting material

siort of the reactor, so only special reactors can be used. In addition, the iodine decomposes the resin acids during the reaction, so that a disproportionated rosin is obtained which has a very low softening point and is dark in color.

When iron iodide catalysts are used, a dark-colored disproportionated rosin is obtained and, moreover, this catalyst acts about 0.01 to 5% by weight of sodium iodide and / or corrosion of the reactor.

Potassium iodide, and the invention was therefore based on the object of a

Process for the disproportionation of rosin and / or polyunsaturated fatty acids for To provide that does not have the disadvantages mentioned above, the catalyst does not through

Sulfur or sulfur compound that is in the too

disproportionating material are contained, inactivated or poisoned and where ί ^ · Λ at the

The invention relates to a catalytic process for the disproportionation reaction no poisonous gases de-disproportionation of rosin and / or more winding. The catalysts used should the polyunsaturated fatty acids at elevated temperature. The reactor does not corrode and there shouldn't be any The rosin is a natural product that is found in catalysts, e.g. B. by sublimation in the Disproportionation reactions occur primarily from abietic acid and similar resin acids. Furthermore, solmit a conjugated double bond and pimaric acid, len in the process of disproportionation of Isopimaric acid and similar resin acids with a colophony and / or polyunsaturated fat-conjugated double bond consists. The colophonic acids are obtained as uncolored reaction products and the softening point of these products should be reduced as little as possible.

The object is achieved by a method of

lophonium and tall oil rosin. It is known that the type specified at the beginning, which is characterized Resin acids with conjugated double bonds, which is that the reaction at i 50-300 ° C in the presence

of a catalytic converter A) about 0.01 to 5 wt .-% sodium iodide and / or

nium can be of three different types depending on the extraction method or the preparation process be classified, namely rosin gum, wooden

It contains rosin, especially abietic acid, which interferes with free radical polymerization, if that Rosin is used as an emulsifier for the production of styrene-butadiene rubber, ABS resin or chloroprene rubber in emulsion polymerization. Hence the soaps of the so-called disproportionated rosin, in which the conjugated double bond is replaced by a disproportionate

Potassium iodide and B) 0.01 to 5% by weight of iron, iron oxide, iron hydroxide and / or iron sulfide, each based on the

Source material, consists There were experiments with sodium iodide and potassium jo-

elimination reaction has been carried out on an industrial scale in 40 did and found that these iodides Used extensively, they have very poor catalytic effectiveness

In addition, linoleic acid, linolenic acid and and are unable to make rosin too similar polyunsaturated fatty acids or misproportionate and thereby a large amount of mixtures of these acids with rosin, e.g. B. tall oil, abietic acid remains in the reaction mixture In a similar disproportionation reaction, it was found that metallic iron and iron are added to produce products which bind as emulsifying agents, such as iron oxide, iron hydroxide and iron sulphide, are used in emulsion polymerization and are completely inactive as disproportionation catalysts can. are. It was therefore surprising that the iodide (A) and

In the disproportionation reaction, the iron compound (B) is used together as disproportionation rosin, generally in the presence of a catalyst; can and do Catalyst, e.g. B. from palladium, nickel, sulfur, a complete disproportionation of colophony selenium, iodine and iron iodide warms palladium and im is achieved without any proportions However, nickel catalysts have the disadvantage that they remain abietic acid in the reaction mixture. Inactivated by sulfur or sulfur compounds, it was found that the iodide (A) and the and therefore these catalysts are for the iron compound (B) when these compounds are used together. B. Effect linoleic acid and linolenic acid. In addition, it was found that mixtures of rosin 60 and polyunsaturated fatty acids, e.g. B. tall oil, can be effectively disproportionated in a similar manner can, if one uses this catalyst consisting of the iodide (A) and the iron compound (B) When the two above 65 compounds are used together, a synergistic effect surprisingly occurs.

The iodine compound (A) and the iron compound (B) are used together for the

contain several 100 ppm of sulfur, not suitable. In addition, these catalysts have the further disadvantage that once they are used for the disproportionation of rosin gum or wood rosin, they are no longer used again

can be used.

Sulfur and selenium have the disadvantage that they are poisonous during the disproportionation reaction Develop gases, e.g. B. hydrogen sulfide or hydrogen selenide.

Iodine tends to sublimate and therefore sublimation losses and corrosion occur during use.

Process according to the invention not poisoned or inactivated by sulfur, so that a very effective Disproportionation of tall oil or tall oil rosin, tall oil fatty acids and that of tall oil Conductive acids or compounds is achieved. In addition, the iodide compound (A) and the Iron compound (B) can be used again after the recovery. In contrast to the usual Process in which an iodine catalyst is used, the problem arises in the process according to the invention the sublimation of the catalyst and the corrosion of the reactor do not occur. In the method according to the invention no toxic gases are evolved. The disproportionated product produced in the process according to the invention is only minimally colored The method according to the invention also has the advantage that the rosin can be disproportionated, without the resin acids being correspondingly decomposed and the disproportionated product being strong When the method according to the invention is applied to tall oil there is an exchange of hydrogen between the abietic acid and the polyunsaturated fatty acids in tall oil, whereby dihydroabietic acid and monounsaturated fatty acids are formed first without abietic acid or polyunsaturated fatty acids in the resulting reaction mixture lag behind. In the process according to the invention, the polyunsaturated fatty acids result in a mixture of monounsaturated fatty acids and Dimers or trimers of polyunsaturated fatty acids, this mixture if it continues is distilled, monounsaturated- · fatty acids of high purity that have little or no multiply contain unsaturated fatty acids, -Jt

As starting products are z. B. rosin gum, Wood rosin and tall oil rosin suitable as polyunsaturated fatty acids are linoleic acid, Linolenic acid and tall oil fatty acids, linseed oil fatty acids, cottonseed oil fatty acids, rapeseed oil fatty acids and soybean oil fatty acids are suitable, the large proportions of these Contain acids. As a mixture of rosin and polyunsaturated fatty acids, e.g. B. tall oil suitable, whereby such mixtures can contain unlimited proportions of rosin and polyunsaturated fatty acids.

The iodides (A) used according to the invention are sodium iodide and potassium iodide, which also together can be used. These iodides (A) are in the form of particles or crystals of the usual shape The iodides (A) are expediently used in an amount of about 0.1 to 2% by weight, based on the to disproportionating material, used when the iodides in an amount of less than 0.01 wt .-% are used, the disproportionation efficiency is reduced, and if more than 5 is used % By weight, no noticeable improvement in the process result is achieved. The iodides are in the generally on a suitable carrier, e.g. B. applied coal or alumina in the usual way.

Suitable iron compounds of group (B) are metallic iron, iron oxides, iron hydroxides and iron sulfides, it being possible for at least two of these compounds to be used in combination. Examples of suitable iron oxides are Fe ₂ Oj, Fe ₃ O * and FeO. Examples of suitable iron hydroxides are Fe (OH) ₃ and Fe (OH) ₂ . Suitable iron sulfides are, for. B. FeS and Fe ₂ S ₃ . The iron compounds of group (B) are preferably used in the form of particles or in powder form. The particles have a size of less than 2 ^ mm, in particular less than 0.5 mm. The iron compound (B) becomes appropriate in an amount of 0.1 to 1 wt .-%, based on the to disproportionate material, used when using an amount less than 0.01 wt% the disproportionation effectiveness is reduced essential while using a lot of

ίο more than 5% by weight, if possible, no noticeable Improvement of the activity occurs The iron compound (B) can also be on a carrier material applied, e.g. B. on carbon, aluminum oxide or similar materials.

η The inventive method can in one carried out in an open or closed container, batchwise or continuously will. The method is not limited in the manner such as the iodide compound (A) and the iron compound manure (B) to the material to be disproportionated, the is called the colophony, the polyunsaturated fatty acids or the mixtures thereof is added. So z. B. a mixture of the iodides (A) and the iron compounds (B) to disproportionate added to the material. It is also possible to add the iodide (A) and the iron compound (B) as separate materials. The implementation is carried out by dispersing the catalyst uniformly in the material to be disproportionated

jo will. The reaction is generally carried out at elevated temperatures, conveniently at a temperature of about 180 to 28O ⁰ C for a time of about 1 to 8 hours. At a temperature below 150 ^° C., the reaction proceeds with a very low rate Speed from, while at temperatures above 300 ⁰ C an undesired decarboxylation occurs. It is preferred to carry out the reaction under nitrogen, carbon dioxide or a similar inert gas atmosphere. After the Implementation of the catalyst is carried out in a conventional manner, for. B. by filtration of the disproportionated product severed.

The product produced by the process according to the invention is a soap that is used for the emulsion po- lymerization, especially as an emulsifier, can be used when the product with alkali, z. B. Sodium hydroxide, potassium hydroxide or similar material is neutralized. The method of the present invention is as follows with reference to the examples and the comparative examples explained, the percentages being percentages by weight. The resin acids and fatty acids were analyzed and the proportions of the materials and products were determined by the following methods:

1. Determination of the composition of resin acids and fatty acids

The total resin acid content and the total fatty acid content were determined in accordance with ASTM D1585-63 The amounts of the components that are contained in the resin acids and fatty acids have been determined determined by converting the resin acid or the fatty acid into the methyl ester using diazomethane converts and gas chromatographed the ester (column 3 m long and packed with diethylene glycol succinate (DEGS) at a temperature of 200 ^° C.). The proportions of the components are expressed in percentages by weight based on the total weight of the material or

Product,

2. acid number

was determined according to

The acid number
ASTM D 465-51,

3, softening point

The softening point was determined using the ring-and-ball method certainly.

4. Coloring

The potassium salt of the disproportionate product is formulated as a 25% aqueous solution and the Color of the solution expressed as a unit of the Gardener color scale.

5. Iodine number:

The iodine number was determined according to ASTM D 1959-61.

! fti B e i s ρ i e 1 e 1 to 4

rS in a Vicr neck flask were 200 g Taüölkolopho-

':' ■; nium with the properties given below

| $ given and then the ones given below

Ιλ amounts of catalyst are added and the mixture

{? · With stirring for 4 hours at 220 ^° C. below

: heated flowing nitrogen gas. After completion

i: The catalyst was filtered off hot after the reaction

if and the reaction mixture is cooled.

Properties of tall oil rosin:
Acid number 178.7

Softening point of 67.0 ^p C

Resin acids 91.1%

(containing 16.4%

Dehydroabietic acid

and

39.2% abietic acid)
Fatty acids 43%

Neutral substances 4.0%

Table 1 shows the types and quantities (in

% By weight, based on the tall oil rosin) of Catalysts used, the properties and the

is composition of the disproportionate product summarized

Comparative examples 1 and 2

The disproportionation reaction will be in the same Carried out as specified in Example 1, but with the exception that iodine 'Comparative Example 1) or sodium iodide (comparative example! 2) in the in Table 1 indicated amount is used.

Table 1 shows the type and the amounts (in wt .-%, based on the tall oil rosin) of the catalyst used and the properties and composition of the disproportionated product.

Table I.

example example example example \ borrow Comparison I. - 4th example 1 example 2 catalyst Art NaJ + Fe ¹ ) NaJ -t- FcO, NiJ -r Ic (OHi-, NaJ - FeS J, Well Amount (wt .-%) 0.5 + 0.3 0.6 + 0.2 ' Ot · ■ + - 0.2 0.6 + - 0.2 0'.4 0.5 product Acid number 166.3 166.3 167.5 169. " 167.3 166.5 Softening point (° C) 59.0 57.0 56.5 56.0 41.0 51.0 colour 4th 3 4th 4th <■) composition Resin Acids (%) (total) ■ 85.1 84.5 S4.3 84.2 80.6 82.0 DehyiJroabietic Acid ("A) 47.4 44.2 44.6 44.1 27.2 7.3 Abietic acid ("A) 0 0 0 0 2L9 Fatty acids ("A) 4.2 5.3 5.1 6.8 8.9 7}

¹ l iron powder

ίο

The results of Table I show that the method of the present invention effectively disproportionates rosin, completely eliminating abietic acid from the product, while the conventional method using iodine does not remove abietic acid. When sodium iodide is used alone, a large amount of abientic acid remains in the product and, moreover, the disproportionation is insufficient. The process according to the invention leads to disproportionation products with a minor reduction in the softening point of the starting material and a slight discoloration, while the use of | od or sodium iodide / u results in a considerable reduction in the softening point and a considerable discoloration of the product.

Examples 5 to 8

ts became 2öög Taiiöi and a certain ivierigc of the catalyst was placed in a four-necked flask and the mixture was stirred at 250 "C for 3 Heated for hours with nitrogen gas being introduced into the flask. After completing the implementation the reaction mixture was separated from the catalyst and cooled. In Table 2 are the properties and the composition of the disproportionate product and the types and amounts of those used Catalysts summarized.

The tall oil used had the following properties:

Acid number 184.6

Flarz acids (total) 54.7%

Abietic acid 20.8%

Dehydroabietic acid 9.5%

Fatty acids (total n> i) 41.9%

Linoleic acid 8.2%

oleic acid 16.3%

Comparative Example 3 The disproportionation reaction in the

giciCMCM manner "as iit uCfi fiCiSpiClcn 5 r / iS 8 performed with the exception that potassium iodide was used.

In Table 2, the type and amount of the catalyst used and in the analysis of the Results obtained product are summarized.

Table 2

iicispici example example example Compare 6th 7th 8th example ." catalyst Art KJ-I-Fe ¹ I. KJ + Fe, (), KJ + Fe (OlI), KJ + FeS KJ Amount ((iew .- 'i) 1.0 + 0.5 1.0 + 0.5 1.0 + 0.5 l.n + 0.5 1.0 product Safety number 165.5 167. ' 166.3 165.6 164.8 Nar /. Acids (%) 49.5 49.7 48.9 48.6 46.9 Abietic acid (%) 0 0 0 0 10.9 Dehydroabietic acid (%) 31.0 30.2 28.5 32.0 24.9 Fatty acids (%) 37.1 37.7 38.1 38.0 39.2 Linoleic acid (%) 0.5 0.4 0.4 0.5 4.1 Oleic acid Γ '») 33.2 34.1 33.7 34.3 21.2 ') f-iscnnuKcr

The results of Table 2 show that the process of the invention when applied to tall oil completely removes the abietic acid from the resin acids contained in tall oil, primarily dehydroabietic acid and also oleic acid, a monounsaturated fatty acid, being formed. In contrast, if potassium iodide is used alone as a catalyst, the reaction product still contains abietic acid and only a small amount of monounsaturated fatty acids.

Examples 9 to 12

200 g of tall oil fatty acids and certain amounts of the catalysts were placed in a four-necked flask and then the mixture was ^{heated with stirring at 220 °} C. for 3 hours, nitrogen gas being passed into the flask. The reaction mixture was cooled and then distilled, a fraction being collected at 190 to 200 ° CV333 mbar. Table 3 summarizes the analysis results of this fraction, the yields in relation to the fatty acid starting material and the types and amounts of the catalysts used. The tall oil fatty acid used as the starting material had the following properties:

-> n iodine number 157

Acid number 195.9

Resin acids 1.9%

Fatty acids (total) 965%

oleic acid 31.1%

Linoleic acid 41.5%

Linolenic acid 2.9% Cig conjugated dienoic acid 2.2% Comparative example 4

A disproportionate reaction was carried out and then the product was distilled and in the same way as in Examples 9 to 12, with the exception that only sodium iodide was used as the sole catalyst.

Table 3 shows the analysis results of the fraction, the yields in relation to the amount used Tall oil fatty acid as a starting material and the type and amount of catalyst used are summarized

Table 3

He example he example
III

Hot example
Il

Hot example

ι:

Comparative

catalyst NaJ f le ¹ ) Art 0.5 + 0.3 Quantity (weight- ⁰ ,:,) product 78.5 Yield (":.) 8 ~ J (Kl number 1 «-Ϊ2.5 Acid number 0 Resin acids (",.) Fatty acids 75.1 Oleic acid C ¹ -) 0.1 Linoleic acid (%) 2 2 Linolenic acid (M. 3.4 C _1x conjugated dienoic acid C) ¹ 1 IvisenpuKer

NaJfIcO ₁ NaI + 1'ciOH). NaJ + IcS 0.5 + 0.3 0.5 + 0.3 0.5 + 0.3

IN THE. ¹ '

"4.3
0.2

"\ P.3

"" 3. ft
DI

3.4

"X.5

(1.2

NaJ 0.5

121 I'M.2

45.4 0.1

Table 3 shows that the erfindiingsgemäße Process using fatty acids as starting materials to produce monounsaturated fatty acids in high purity that are polyunsaturated fatty acid free while at the sole results Using sodium iodide as a catalyst is just a mixture of unsaturated fatty acids that is a great one Contains amount of Qg conjugated dienoic acid that is, no effective disproportionation is achieved in this case.

Application example

The disproportionated products obtained by the procedures of the preceding examples (see Sect. Table 4) were neutralized with potassium hydroxide to produce the corresponding soaps, which then have been investigated for their properties as emulsifying agents for emulsion polymerization.

For this investigation, the following compositions were placed in a pressure reactor, in which they were cooled ^{to 5 ° C.} 0.05 part by weight of p-methane hydroperoxide was then added to the reactor and the mixture was polymerized at 5 ° C. for 8 hours with stirring. Finally, 0.05 part by weight of sodium diniettuldithiocarbamai was added to the reactor in order to stop the reaction.

Styrene

Butadiene

Sodium formaldehyde sulfoxy

lat 2 H; O

Iron sulfate · 7 H »O

EDTA tetrasodium salt /

Sodium phosphate I2U.O

Natriuninaphthalt.usulfonai-

formaldehyde condensate

Dodecyl mercaotan

Emulsifier

deionized water

ISGeu. Parts 35 parts by weight

0.075 parts by weight 0.025 parts by weight 0.05 parts by weight 0.400 parts by weight

0.075 parts by weight 0.100 parts by weight 2 parts by weight 100 parts by weight

The styrene-butadiene latex obtained was steam-distilled. to remove the unreacted monomers. The implementation of the monomers to the Polymer was determined according to the following equation:

Conversion (%> = -Ü £ ^ ^{hl ü} - formed polymer
Weight d. used monomer C

100.

The results are summarized in Table 4.

In comparison, a common emulsifier of the disproportionated rosin type (Rondis, was prepared from rosin gum) in the same manner as indicated above, examined and the achieved Conversion was calculated analogously. The results are summarized in Table 4.

Table 4

Application Disproportionate Product Conversion example as an emulsifier

Product of Example 1 63-5

Product of Example 2 62.8

Application * - DispruportionieriCN Pnxlukt l'muandlunc example jIs emulsifier

Product of Example 3 62.5

Product of Example 5 62.5

Product of Example 9 74.6

known emulsifier 62 J

d
e

Comparative experiment

The results of Table 4 show that the emulsifiers obtained from the inventively prepared disproportionate products have been made, more effective emulsifiers for emulsion polymerization are known as the emulsifier.

Claims (1)

Claim: Catalytic process for the disproportionation of colophony and / or polyunsaturated fatty acids at elevated temperature, characterized in that the reaction is carried out at 150 to 300 ⁰ C in the presence of a catalyst from A)