DE1618397A1 - Process for the production of color-improved and color-stable nitrogen-containing fatty acid condensation products - Google Patents

Description

FLBBWERlE HOEGHSf AG. ₉

formerly Meister iueiijs & Brüning Br, Br «/ Mtl ?,

I Qd 1425

Description for

Patent application

" Terfahren . For the production of color-improving agents ^ in the d fcolor-stable nitrogen-containing Pett Bjäure ~ gpndffieatip ^ s-ßr, g . Dukte"

Biologically degradable Eosdensationsprodukte iron! Fatty acids with alkanolaninea and their derivatives, ζ «B ₉ -dl © obtained by the addition of alkylene oxides of @ Ti® have in more recent times as beneficial substances on £ 2, tisaig @ n. H dishwashing detergent » _ff where they as Schaua @ taMli @ afQr: 6 & isnä.

early as free net fabrics. really _? © ö ^ r als i'fesässmfetöffe

Acquired again Beäei & tuBg. -.

Her over the $ tÄIXtt "ir Oer Fettsä'ßiie & OBSosiistionsp ^ öäukt © IAIT AUcanolanineis 1st since öen- gifEBÄJegsaden work ψοπ in 1957 ^^ C @ st at © efes? Ift§n 2,089,212 usä 2096745} gearbÄet wqxüb & * Sg fesi Ie ^ direct g

with Alkaaolsssiaea hßh @ Ssm ^ s2? © ti5r © s ^ © rf OErdtrlieli sisd _s so int this the f £ t% ll.s% ei $ Mm lilSimg tob Sitlwiiso ^ sdcten. is given a high base. Ale @ © Iüh © <jsla & I »si3 * 8e-nd @ ^ ® die amines, 4aiid« et «7 and H ^ lmltlgsn Polj'-s.ljkolt zi:% ®imep. _f You and STtseftteBrngeB from the

is ^ esf.

»It aes

Even if such an iminolysis in the exchange of the fatty acid for its ester significantly improved products compared to the direct conversion of fatty acid with alkanal. amine is preserved », in some cases they still leave something to be desired with regard to their farhe, which still prevents their extensive use in various fields of application. This applies for example to the "osmetiksektor where they _t kÖnaten as substitutes for other biologically serve poorly degradable raw materials for '-' anäe $ e can also!" In the above-mentioned Cteall ^ lieruiig T © n fatty acid alkanolamides amides occurring 3? arbveraehXeehterimg iter @ n Sinsatz als WasehmitteHEQmponesrfc®- «as Ia; Isasehraktem HaSe zu ·

* It therefore looks aa ¥ @ «« itei / gef echte »by adding certain

Inhibitors during the preparation or during their preparation (OxäthjXi © Eissg) this lTerfäriiungen to yer- J & W9Xt- Yes measures comes - insofar as "special care t0- shown. ϊertigproduIrCeB 'through' the ü'ijllcfrsr; Hatred - such as lead depletion - with hydrogen superosyte *. only -wsl ■

led.

In the group of peculiar luhiiiitors, who have shown benevolence in many other cases, belong to the group of hindered Biftnol "Cp" te "t.Bat3rlpae? I © l. »Jon®!) Or JfeöBphit» and d # rgleicheil j & evm Mmenäwag in eem-present case but none

On be »t ^ i, ^ <3VIQirt0 siea still, the Ec ^^^^ & tioii described in ö # r 1 090 435 before; Kydraaeinhydrat and rpViOßpVior.lgsr acid, they in fleicliiaolRrön amounts sum a. g@3.aQgen «. Be and Mar ^ qIX significant improvements in doors

prifct4s «fe fe ^ blQ« «^ S! rodtflctt» »ti« a bei sät »Tsci & ·· § #» QaEitfty? .at «a _t xurde» uch Uli Äteeoic tfcn & ismfo & SS nests TölSirli ».tift cs ^ t. ' sÄii * % w & m ind

Cc, -er. ic-

the alkanolamine or the fatty acid, au. So describes . the 'German patent 878 542 the addition of sulphurous acid

au triethanolamine Tor whose conversion with fatty acid »Bas Yerfahren provides excellent color-stable triethanolamine fatty acid soaps, which show little tendency to discolouration even after long periods of storage Alkanolamines for the production of fatty acid alkanolamides, however, go beyond the stabilizing effect of sulfurous acid at the high temperatures required here, they are soon lost, and in no way improved products are obtained. ·

The German AusleJseschrift-1 124 962 should also be mentioned as belonging here _9, which achieves the same goal by adding glycol instead of SO ₂ . © tries to reach. · ". '■

The second component "remains the fatty acid or the fatty acid ester and its purification in order to achieve color-improved and color- © stable probe products.

The refining of fatty acids by treatment with suitable absorbents has been known for a long time ₉ and the use of bleaching earth of various types is found in all current handbooks. For example, in a prospectus of the Süd-Ofeeinie (M. & g & .he 1962) there are references to the optimal use of different raw materials, common to all working methods is the ¥ © s? S © lirift _f in dae to the selected bleaching « stir the bleaching earth aperatur vorerMtste hat and \ "gnash best Burclaaipeliung and © iaer certain linwirkungs- aoit. carrion Bleicshmitiei dmrok ^ iltgation separate again. In pflaaslicheB nsüä" feiesiscsSiGa §L © a tm.d Fs ^ t @ a ₉ sm ^ .en & n · The. ^: In this case Increase in brightness © o © "6atea-SaotoOarea or = d © r © n Sstsr ^ge"; foal hear vjesäea as BlQi ^ feteapasiatms-ea TO · "$ § ^ö 0 ss ^ For the BefeaMiiEag voa -. feoetetisefeea Eisasatsgröä ^ tea x-jöstea aiieh "■ '.. ^:: height ^ & iS@sigQ3Sätai^iosOil.efe® s ^ lo ^ feea 150 mad 1 © Ö ^ 0 ^ © sgs-; .-' beat * .-

BsM 7 »ieite 592 gissdet © l @ fe ate ¥ orschrift-s ^CI Uas S ¹ StI; % iird

"- ■ ♦:

20 "- 45 minutes at 70 - 80 ° C with for example 2 -. Stirred 5% bleaching earth and filter presses, the bleaching earth is filtered off ¹¹ on page 503 Ie also a continuous bleaching process is described in which the mixture of bleach goods and bleaching material of the is subjected to a short bleaching time corresponding to an elevated temperature between 105 and 163 ° G.

Kirk-Othmer, "Encyclopedia of Chemical Technology" (The Interscience Publishers, Inc., New York), YoI. 6, page 162 are as common bleaching temperatures 104 - 116 ⁰ C specified. Here, too, the bleaching agent is separated off by filtration after the bleaching process.

The use of fatty acids refined in the known way or fatty acid esters, however, did not bring about the necessary substantial improvement in color due to condensation Fatty acid alkanolamides obtained from alkanolamines. In particular when processing them to non-ionic oxyethylates always further deteriorations in color are accepted.

It has now been found that the color can be improved and color stable Fatty acid alkanolamides and their oxyalkylates from fatty acids or their esters by reacting them with alkanolamines and, if appropriate, subsequent oxyalkylation can be prepared by adding to the - possibly by prior melting liquefied - fatty acids or fatty acid esters before condensation with the alkanolamines natural and / or artificial Stir in bleaching earth, the mixture obtained is heated to boiling in vacuo, refluxed for a long time, the fatty acids or fatty acid esters are then distilled off from the mixture without prior separation of the bleaching agent and then with alkanolamines and the alkanols obtained from them amides, if appropriate with Qxalkyllerungammittel in a known manner uasetst, "

Take care of the fatty acids pretreated in this way or Fsitsto-eseter alö Auagangaproaiüetβ werfi *! i colored vaxfe · aserfce and especially with respect to thermal

color stabl. Fatty acid alkanolamides! Saw. get their ox & fchylate. _ / ■■■■ '. · ^: ■>"_-__.

0 0 »8 2 97 1.9'4 Ο 'BAD ZnmiUAL

V: 5 -

1fl8397

essential difference; of the present process with regard to the bleaching of the fatty acids and fatty acid esters used as starting materials compared to the previously known processes lies in the fact that the lead agent is not removed from the bleaching mixture after the bleaching has taken place (for example by filtering), but is left in it and the bleached fatty acids and fatty acids ireester ms the mixture, the bleach-containing are distilled off, where ü & a bleaching agent together with back bleibte ^ Verunreinigungenals Destillationsrückstancl

The technical progress achieved according to the process is insofar Surprising and was not to be seen as troubled as in all of them described working method of the technology of fatty substances the bleach through. Kltrai ^ ion was separated and so too contradicts other customs, © in AbsorptiOnsmittel to be left in the product at such high temperatures as to run the risk of being adsorbed. Verimreini @ pleasant at the high Temperature by desorption again in free shark! And spoil the cleaned goods again *

The outstanding deficiency of the present process is not only evident in the color of the fatty acids or fatty acid esters obtained in this way, which can also be improved by known measures, such as distillation or conventional lead processing, but generally only in the case of subsequent animals condensation zn the Fettsä ^ urealfcanolamiden: ima even more so for their further reaction with ÄlkVlenoxyden: färbverbesserten m Ijeeonders, and color-stable Qxalkylaten.

The following examples relate to the cleaning of fatty acids, mainly based on the conversion of fatty acids with alkanolamine - in the ßegsnsmtis su den fatty acid ^ SÄ ^, better products are obtained from the start ... The w _: eit © r®: -Ussetsuiig-, the fatty acid ester and .Al & anolaffiln® ^ 4

amides occurs xiaeh

in the patents listed above will.

B e i β P i e 1 1ϊ

In a 4-inch, 4-neck, round basket, equipped with a stirrer, Vacuum capillary for nitrogen ventilation * Contact thermometer and Reflux condenser, 2 kg of tallow fatty acid are submitted and after the melting with thorough stirring 40 g (2 #) highly activated

CnS

Fuller's earth (TONSIL ^ .6O -C) added. Then an oil vacuum pump is connected and in 1 - 2 hours to the boiling temperature corresponding to the vacuum; heated by 230 ^{0 G.} The fatty acid is kept together with the bleaching agent by stirring with the nitrogen sucked in through the vacuum capillary, finely divided, heated under reflux for about 2 1/2 hours and then the tallow fatty acid is distilled over a short distillation bridge with a drip catcher without first removing the bleaching earth away. After removing a small, darker-colored forerunner (about 20 ml), the tallow fatty acid is obtained as a yellowish-white, narrow product (iodine color number 2.0).

The one produced therefrom by reaction with monoethanolamine Tallow fatty acid monoethanolamide had the iodine color number 16. On off an untreated tallow fatty acid produced in the same way Amide, showed significantly poorer color values.

Joifarbgahli

Fatty acid monoethanolamide

Tallow fatty acid, unsealed 2.0 35

η Φητϊβττ »_>» ΛΐΐΩηιΛβΤ + 2.0 16 *

at Massitz of fatty acid

@ 8i; © £ n © sisttll © Y © af @ttiiteea _s like makst & XX® arwähnt ₉

with 2 '$ TONSIL Lf ί? 80 In the described vieiseyor treated "(reflux temperature 170 ⁰ G, transition temperature fi @ s Taigfettsäuremethylester 170-19O ⁰ G at " Q - 10 Sorr |. © itTakuuii). The ester purified in this way was converted by using ethanolamine with mono ~ "ethanolamine. The Taj _: gfjettsäuremonoätfeaäOlgmiduna

"about what can be achieved with the claimed disobedience progress particularly clearly, i «earth in the next table next to the. «^ treated .. fatty acid ester also iaaide and partly also their Oxäthylate einbesögen, for their Production of a tallow fatty acid ester was used »the by simple distillation,: ~ that is, without the invention TONSIL additive, obtained ^ urde ^ -. Tinfl. '"Of the" further tallow fatty acid ester, -die with TONSIL ia ter the usual Weis® cleaning by stirring in the BleielÄittal at the given Temperatures, 1/2 hour. Stir-and ... subsequent-filtration at different temperatures. «- Tuck searches correspond to the state of the art. "

BAD OBIGJNAL

- ■ 8 -

Source material

Iodine numbers:

Amid + 10 Mole AeO color stability test original after 120 hours / 60 ° C

Tallow fatty acid methyl ester untreated

Freshly distilled
(without TONSIIr addition)

usual TONSIIr cleaning

Stirred for 1/2 hour and filtered

2 % _ TONSIL 60 C / 7O ⁰ C 30 % TONSIL 60 C / 7O ⁰ C 2 fo TONSIL LFF 80 / 7O ⁰ C 5 % μ ■■ ^Λ 5 f "

Il
It
Il

«/ 100" C / 150 ⁰ C / 200 ° C 2 hours. / 10O ⁰ C

Il
It

cleaned with 2 # TONSIL ΈΕΈ 80
according to example 2

55 20

30 10

20 18 16 16 16 18

1.5

90
70

2.0

In particular, the preparations obtained from the ester purified according to the process show a surprising parstability under thermal stress. Stored for 120 hours at 60 ⁰ C - - After a prescribed for such Oxäthylate of the detergent industry Parbstabilitätsteat the color of the Oxäthylates from the original value has risen only to iodine color 2 1,5, that remained virtually unchanged (column 3 and 4 of the Table) "

According to the present procedure, therefore, specifically at particularly color-stable fatty acids achieved surprisingly good effects compared to the known pure casting process.

GQ9629 / 1940

BAD ORfQJNAL - 9-

IS18397

For example I 5: /

In the same apparatus as described in Example 1, 2 kg of coconut fatty acid methyl ester (Cq-C ^ q) are treated with 40 g = 2 fo TONSIL IPP 80 »"

The Rückflußtemperatürbei a water pump vacuum of 12 Torr was 10O ⁰ C and the mixture of esters and TOiISIL was obtained for 3 hours at this temperature under reflux at the boiling point. This was followed by distillation * 'again without prior removal of the TONSIL. In a boiling range of 115-150 ⁰ C / 9 - the use amount of 97% as a completely colorless liquid - 12 Torr temporarily, a small Torlaufmenge of about 10 Cocosfettsäuremethylester with a yield of 95 was after removal ml. The coconut fatty acid monoethanolamide obtained therefrom by condensation with monoethanolamine has an iodine color number of 1.5; the coconut fatty acid monoethanolamide + 10 AeO produced by the addition of 10 moles of ethylene oxide has remained the same light (^ od color number 1.5) and has also passed the color stability test with excellent results.

If one same Cocosfettsäuremethylester but in the same way without the t-described TONSIL treatment, are reacted to give the amide and Oxäthylat so much poorer Parbzahlen be obtained as the following comparison of the various Pahrweisen proves

Source material

Iodine Parb Numbers

Ami

Uexi

IO Mol AeO

For beta test Original after 120 hours /

Coconut fatty acid methyl ester untreated

with TONSIL LFP 80 cleaned

15.0 2.0

00982 971940

BATH ORIGINAL 10 -

A corresponding commodity - lauric acid monoethanolamide -. Shows a Parb number of 9.5 and its oxethylate even one, those of 90.0.

Example 4:

In the same way as described in Example 3, an oleic acid methyl ester was again pretreated with TONSIL LPP 80 (2%). The reflux temperature was in this case at 143 to 145 ⁰ C at 12 Torr, and the ester was boiled for 3 hours at this temperature together with the TONSIL under reflux. The TONSIL was then distilled off and the oleic acid monoethanol amide and its oxethylate were prepared from the ester with 10 moles of ethylene oxide and the analogous products were used. compared to untreated crude ester:

Source material Iodine Parb Numbers: Amide + 10 moles of AeO Llity test
after 120 hours / 60 ° C Amide Color stick.
original 15.0
2.0 oleic acid methyl ester
untreated
with TONSIL LPP 80
«Ereiniet 8th
.Ϊ.5 9.0
1.5

As the following examples show, the process carry out larger batches with equal success.

Example 5;

In a 30 l Leetlllationeblaae made of glass 15.6 kg TaIgfetteäuremethylester were stirred with 0.32 kg TONSIL LFF 80, heated to the boiling temperature of 170 ° C at 8-10 Torr reflux, refluxed for 3 hours with the TONSIIt and, voa TONSIL then in a settlement terrall of 170 - 190 ⁰ O / 3-3Dltrr of the Eitea? Completed. .

"14.4 legs of purified tallow fatty acid esters", that is 92 % of the insert, were obtained. The residue remained 1.2 kg =

s φ . ■■■.-.'_ .- ⁷ ; ■ - ■ - ■ .. ■; V-- '■■ -. .

The g ^ i'At ^ ig ^^ t'PTiioTLaäifliaTininmiii was prepared from this ester in a V4A stirred tank in the manner described several times with monoethanolamine and sodium methylate as the condensing agent, and this was then immediately reacted with 10 mol of ethylene oxide to give TaIgfatty acid monoethanolamide (+ 10 Ae) 5 kg), the following JTarJaqualitat was obtained:

Iodine Parb Numbers:: Amide + 10 moles AeQ ■ ---- ■ "."
ν ;;;: /: 4 * 0-, - ^; - ■ Source material Amide Parbstahltätstest ■ · _ "
Original according to ISO -Std./60 ⁰ C '1.5 ^; Tallow fatty acid mono
ethanolamide 4.5

B is ρ ie 1; 6; . ,

In the same way were cooking kg Cocosföttsäuremethylester 0.31 ° f IFF TOIiSIIt 80 "for 15 ^ 5 Luss under Rlickf and distillation of the ester were performed as in Example 5, wherein the Rückflußtemperatmr at 115 ° G and the Destiliationstemperatur at 115 -. 150 ° (9-12 Torr) were. "· - '15 _s 0 kg = 96.8 <? O of the input were obtained as a distillate. They gave the following color numbers for the product made therefrom

^ O £ osfatty acid monoethanol®mid s iodine- ^ FZ ■ 1 * 5 "n. 120 hrs * / 60 C i -

+ 1 ieOi 1.0 ■■ - "- ■■. / 1.5

+ 2 »1.0 -" - 1.5,

19th

12 -

ν BAD OHIGiNAL

Claims (1)

Claim; Process for the production of color-improved and color-stable Fatty acid alkanolamides and their oxyalkylates from fatty acids or their esters by reacting them with Alkanolamines and optionally subsequent oxyalkylation, characterized in that one in the - possibly through prior melting liquefied - "fatty acids or Fatty acid esters before the condensation with the alkanolamines stirs in natural and / or artificial bleaching earth, which The resulting mixture is heated to boiling in vacuo, refluxed for a long time, then without prior separation of the bleach, the fatty acids or fatty acid esters are distilled off from the mixture and then these with alkanolamines and optionally reacting the alkanolamides obtained therefrom with oxyalkylating agents in a known manner. BATH 9829/1940