US2607783A - Amidoester waxes and method of forming - Google Patents

Description

Patented Aug. 19, 1952 2,607,783 V AMVI'DOESTERY WAXES AND METHOD F FORMING] Otto Turinsky, Palatine, Ill., assignor'to Armour and Company, Chicago, 111., a corporation of Illinois No Drawing. Application'September 5, 1947, Serial No. 772,472

9 Claims. (Cl. 260-4045) This invention relates to amidoester waxes and the method of forming the same, and more particularly to a synthetic wax having very much the properties of carnauba wax.

A synthetic wax which would substitute carnauba was in the true sense is in great demand and as yet is commercially non-existent. In comparison with carnauba wax, the synthetic waxes to date fall short in several ,ways. Among these may be mentioned, solubility behavior, softening and melting range, gloss, hardness, toughness, and the ability to form tough or durable glossy filmsfwhen rubbed and buffed onto a surface. The latter property, being especially important, is lacking in waxy compounds like the present amides, methylene diamides, hydrogenated glycerides, hydrocarbons, etc. Although the composition of carnauba wax is known at least in a general way, it is not practical to prepare a synthetic wax of the same composition as carnauba because the constituents are scarce and/or dimcult to synthesize.

An object of this invention is to provide new synthetic waxes which tend to be non-crystalline and which possess the property of forming glossy films readily whenmubbed onto a surface. A further object is to provide a method in which culated quantities of fatty acid and alkanolamine there is a controlled alteration of the molecular size-and structure, for obtaining non-crystalline waxes of difierent melting ranges and different degrees of hardness andtoughness, while yet possessing theabove-mentioned desirable characteristics of carnauba wax. A further object is to improved methods for forming such products.

Other specific objects and advantages will appear as the specification proceeds.- 7, "The class of compounds 'whi h makes up the synthetic waxes of this invention are amidoesters. More specifically, these waxes are reaction products of (A) higher fatty acids and alkanolamines;

"and (B) higher fatty acids; alkanolamines, and

polybasic acids or'their ethyl esters. By higher fatty acids or high molecular weight fatty acids, I mean fatty acids having fromloto 26 carbon atoms. I prefer to employ fatty acids having from 10 to 22 carbon atomsr-However, all ofthe' (to give a complete reaction) are merely heated together (say about -180 0.), preferably in an inert atmosphere and finally under reduced pressure (preferably about 5 to 15 millimeters of mercury). If desired, the temperature may be ra sed above C. I find, however, that it is ordinarily unnecessary to go above this temperature and that there is no advantage in doing so. The following illustratesthe formation of the simpler type (A) amidoesters:'

' CHzCHiOH OHzOH OH 0 H RC omcmoc-R' 3Hz0 N\ 7 I CH2CHaO( 3R- where R, R, and R" are higher alkyl radicals and may or may not be the same.

7 'I'hepreparation of (Bl-the'amidoesters from the higher fatty acids, alkanolamines, and polybaslc acids or their ethyl estersis necessarily performed in two or more steps depending on the structural complexity of the final product. For the second type (B) of amidoesters the following illustrates their formation:

amass 3 Where the adipic acid may be substituted by any polybasicacid or its ethyl ester. Equation 2 may be written thus:

Ri l-NHoEooEnoH R and B being two different higher alkyl radicals. In order to increase chain length of the molecule 4 process described herein indicate that the mono and dialkanol amines containing at least 2 carbon atoms can be made to respond to the process to produce the waxy compounds which are the main purpose of the invention. In particular, the mono and diethanol amines have been found to give excellent results.

Any'p'olybasic acid or; its; ethyl 5 ester'may be employed, and in the examples: set out below, various specific acids and their ethyl esters are 9 listed. All of the polybasic acids and their ethyl esters respond to give the new series of waxes having the desired, characteristics mentioned, and particularly the characteristic of forming glossy films readily when rubbed onto a surface.

- From what has been stated above, it can be seen that a considerable number of amidoesters can be readily prepared from relatively common starting materials. These amidoesters are all waxy compounds differing from each other in such physical properties as melting point, hardpreviously in this invention.

ness, and toughness. The latter physical properties depend on the chemical composition; a factor which isreadily'controlled as described with one mole of an alkanolamine and the resulting hydroxy compound.- again reacted mole per mole with a dibasic acid as shown in (4)., etc., the

proces s'of alternate mole per mole reaction of alkanolamine and dibasic acid being repeated until it is desired to bridge? the resulting hydroxyl or carboxyl compounds. If the last reactant in the chain lengthening process is an alkanolamine,

thus giving rise to a compound with a terminal.

hydroxyl group, then such a compound is bridged by reacting two moles of it with one mole of dibasic acid. On the other hand, if the terminal group of the compound to be bridged is a carboxyl, then two moles of such a compound:

arereacted with one mole of an alkanolamine.

Dialkylolamides (HO CHzCHzl-XTCHzCHzOH where R. is an alkyl radical) when used instead of 'alkanolamines in the bridging or chain lengthening process impart translucency and lower melting propertiesto the resulting amidoesters. Increasing the chain length'in general increasesthe toughness of theproduct. ,As may be seen from what has been stated above, one may use several; different alkanolamines and; al-

kylolamides, several different dibasic-acids and several different higher fatty acids in making up one and the same lengthened and bridged amidoester.

Any of the high molecular weight fatty acids may be employed with satisfactory results. I

have obtained especially good results with stearic acid, and also with palmitic acid. All of the fatty acids, containing 10 or more carbon atoms, give the'desired new results set out herein. Such acids are available up to about 26 carbons in chain length.

My experimental results in, carrying out the The reaction to form the amid structuretakes place at temperaturesabove C. and there action to form the ester structure takes place from about 1&0" C. upward, and it' is usually necessary to employ temperature'siin excess'of C.,to complete the r'e'action., However, .tem peratures" in excessv of 240 C. are not re mended due tothe likelihood of decomposition at such high temperatures." If desired, an inert atmosphere may be used in conducting thereaction, but. this is not essential and, most cases, may be dispensed with in commercial operations, Y

specific examples of the process and of the product and of the series of productscovered hereinmiay be set out as follows:

Theldmidoste'r of sfe'aric acid and ethanolamine "713.4 grams of stearic acid and '78 grams of ethanolamine (molecular proportions: 2 stearic acid; lie'thanolamine) were mixed and heated (preferably with stirring) for 1%-2 hoursat 175485? C. in an inert atmosphere. Themixture was "then heatedat -195" C. and 10-15 mm. pressure for 4. to 5 hours and cooled to 130-140" C: under vacuum before pouring out.

This product was hard, clos -e grained, and light colored (light tan It melted at 85 87 .C. and formed a glossy film when rubbed onto a surface ;(suchasbrown paper). I

Ethylol stearamide, whichv was a start terial in'gthe folowing examples," was. prepared asJfQ p Stearic acid. (290 grams) was mixed. with 80-90 cc. (an excess of the calculatedi'of 'eth- -anolamine.; The mixture was heated for zhours at 180 C. in an atmosphere of nitrogen and then for 2.-2 /2 hours at 1 0400. c. and 10-15 mm.

' :messur to remove the unreacted ethanolamine.

The product obtained was a soft 7 light colored solid, melting at 94-9{C.- v

a tar-ace 2 The i'tihido'ester' fethanolalmine and maleic'anhy'dride Molecular proportions of the reactants represented in thermal product were: -Stearic acid 2, ethanolamine 2, maleic anhydride 1.

A mixture of 208.5 grams of ethylol stearamide and 31.3 grams of maleic anhydride. washeated for 2 hours at 150-170" C. and 10-15 mm. pressure. Under these conditions of heating, a rapid reaction set in at 150 C. and the temperature was allowed to '.riseas the reaction ,rate decreased. After cooling to about=130 .C. (under vacuum), l the reaction product' was poured-.intobeakers .to "solidify; At room temperature, it ,wa's'a reddish, fine-grained brittle wax .which formed ,a glossy 'film when rubbed onto a surface. The melting,

point was -72 Ci- The amidoester of '1 adipic acid Molecular proportions. of the reactant vv represented in the final product were: Stearic acid 2,

'ethanolaminem adipic acid'l,

' a 0 2 r c'nnugzqNrwmcm-o-t zgsmu -0-cnicrimngw nm A mixture of 114 grams: ofethylol stearamide and 24.5 grams (theoretical) of adipic acid was heated at a pressure of 10-15 mm. for 4 hours. The reaction progressed rapidlyat 15020;, but (the temperature was'allowed to attain ,180.-C. within an hour and was-maintained at180-190" ior the-next two hours.' It-wasthen raised to 200 -220 C. for theremaining Z'hours. In order to remove any traces of oily and distillableibyproducts, the reaction mixture was heated at 190=-220 C.- for about 2 -hours at:3 to,5 mm. pressure i After cooling 00130-140? C; undervacuum,

" the hot liquid was poured into beakers. v1.At room,

temperature, the productwasautan colored, hard, fairly-tough, fine grained and glossy .wax which formed a glossy film when rubbed onto-.asurface. Meltin'g temperature: 'softened some: at C. and liquified at 98--110 =C. I v 1 )The amidoester of stearic acid, ethanolamine and ,adipi acid,

Molecular proportions of the reactants represented'in the final product were:- Steari-c acid 2, ethanolamine 3,'adipic acid 2. c

5mm acid, ethanolamine and race: ribe/ever, 'it"was somewhat tougher and finer grained (tending towariitranslucency) than the wax of Example, .L

The a 0am mam-e acid, etha'nz'amme and sebacz'c acid Molecular proportions, o'f the reactants repre' sented inth'e final product were: Stearic acid "2, ethanolamine 2, sebacic acid 1.

The procedure in this case was the same as that in Example 3-; except that the adipic acid was substituted by an equal molar proportion of sebacic acid. The final (sebacic) product resembled the adipic product of Example 3 except that it was slightly lower melting and somewhat tougher.

The second step consistedof uniting or bridgingtwo molecules of theabove hydroxya'mide ester-with one molecule of adipic acid through the unreactedhydroxyl, giving: 7 Y

Preparation of compound (A): A mixture of 2 moles of stearic acid and 1 mole of diethanol- .aminewas heated, preferably in an inert atmosphere for /2 hour at-160 C. After this, the

'heating was continued at 10-15 mm. pressure and 140-100 C. Although the reaction appeared to be completed after 1 hour, the process was continued for another hour with thetempera- -A' mixture of equal molar proportions of ethylol stearamide and adipic acid was heated at 1 180'? C. and 10 to 15 mm.-p ressure until bubbling "ceased '(about 2- 3 hours) After coolingto 140 -C.- under vacuum, ahalf molar proportion of ethanolamine' was added and the mixture was heated in'an atmosp nitrogen (at atmbs- I pheric'pressure) for 2"hours at -185 C, and then for 2 hours at 10-15 mm. -pressure"- and -200" C. Thereaction-product was cooled t'd 130-140 C. in vacuoand poured into beakers. The wax thus obtained softened at70-75, liquifled at fa'bout -100 ,and resembled that of Ex- -ah 1ple"3" in 'colorihardn'ess, gloss, and the ability I action):

ture rising to 180 C. On cooling, there was obtained a tan colored semi translucent, waxy solid, melting at 53-55 C.

Preparation of compound (B): The reaction product (A) (1 mole) was mixed with V mole of adipic acid and heated at 10-15 mm. pressure. Water was rapidly evolved at l00-140 C. After heating at 100-140 C. for 1 hour, the temperature was raised to 170 C. during the second hour.

Finally, the temperature was raised to 200 C, for

V; hour (till there was no more evidence, of re- Ajter cooling in vacuo to 100 C., the hot" melt was poured into beakers. The product was a glossy, waxy-solid .of medium hardness and light tan color (quite translucent), melting {at 48: D C. and form d'a glqssy mm whgn 7 Ex: 5 V110 rubbefl; 01 1 07 Surface V r 1 cthamolamineand EXAMPLEV di fli e fil iqfli i The amidoester of stedricwacid, tha z i 5 7 V l w J I: I lug-i and .dietlvcnolamine and cdipic acid DnHflQfNHQHzQHyfl 3- l :ZNHTQQHH? Molecular proportions of thereactants repre- Sented in the, final product were: Stearic acid 3, A mixture of /2 mole of ethy silicate and 1 ethanolamine 2, diethan'olamine l, adipic' acid 2. mole of ethy lol stearamide was heated -at150;1'15

I QHH It 1 =1 V k preparation, it was necessary to pre- Cwuntil ther'e waslno 'moreievidenceiof thegemlupare diethylol stearamide v v I tion of ethylalcoho'l "(about,2hours). cooled p to product resembled'zthe adipicproductoLEXemme 3-in color hardness, toughness gloss, film form- QCHQOH' r ing'properties,vandlmelting'pointuz V A V;

v v H V V. :c' 5 V v \C.H2QH1OH V EXAMPPEM as well vas the ethylol stearamide before hand. The amz'doester ofs'tedrica'c'id, ethanolamzne and The diethylol stearamide was prepared by heati I i pp 'icic cid stearamide and adipic acid was heated at 160- between the free adipic carboxyls,

.:-in previous examples. It resembled the product ing a mixture of equal molar proportions of 'stearic acid and diethanolamine in the .same manner described under the preparation of zeth- I ylol stearamide. 7 1 a A mixture of zmoleoi bo acidand mole mixture of equal molar'proportmns of ethylol of ethylol stearamide was heated at'145 l'5 0C. til no more water wasevolved (2 hours). 175 C. and 10 mm. ressure until the bubbling un 2 ceased (about 1 ho r required) and then at gitg f f i 152; 3 5 2? g z a r1 e wax, meing a, ,1 A I o-r nged a 190 200 C. for another half hour. After cooling glossy filmswhen rubbed Onto w mm I to 140 C. in vacuo, a half molar proportion of diethylol stearamide was added, and the resulting f 2 f f g i i have e mixture was heated at 190-200" C. and 10-15 mm. o f c S t f 'de i the purpressure for 4 to 5 hours to effect a bridging .pose t certain emboqlfments p invention, it 1W11'1 be :understgod that such deta ls may be varied widely bythose s killed inv the art without departing from :thesp rit; Of, r-i ven- -tion." 7 Iiclaim: v V 1; In .a "process con-preparing an-amidiiester wax product. thess'tepsjof-condensing abouta ,1 :to .1 molar ratio oil-a saturated .monobasic fatty Theresulting product was cooled as described 40' obtained in Example 6 in gloss and in its ability to form a glossy film when rubbed onto a surface, ,but it was a little darker in color, less translucent, and liquefied at 7,5-85 C.

EXAMPLE 8 7 acid containingianeeyen number;o,f carbon atoms p within-the range fromtmto-izfi car QnatQms-w The amzdoes f am: acid, ethanolamme an amine selectedfi-romithe. roup-consisting of and aceti i mono and .dialkanolamines. containing at aeast z carbon atoms by heating es'aiidtreactants to about 140 to 240 C. to iormiannalkylolamide, and then onHs -NHcHio HiogcHs l reacting about a 2 to 1 molar ratio of the alkylola- Amixturebf equalmQlafpmPpmms efihylol mide with an aliphatic *dibasic acid by heating .stearamide and acetic anhydride washeated at 1405C, After .hour, a vacuum (10i15 1mm.

j,gradu ally raised to 185 C. and/maintained thus said second-mentioned reactants to about 180 to 24090. tooomplete thereaction.

I :2, r In 'a process f or preparing' anamidoester until theacetic acid liberated in 'the reaction Wax producfc the Stepslqondensmglaboutta i 3 1 molar ratio of a saturated monobasic fatty acid was distilled out (about 1 hour). The cooled o p V v contaimng an even number of carbon atoms withproduct was a tan colored, waxy solid, melting 7 J a 0 m the range from 10 to.-26-ca-rbon atoms with an at 73-77 0,, but it was considerably softer than I that obta in Example 1 amlneselectedi'rem thegroup consistin ofmono a a o 0 and methanol amines by heating said;reac.tants EXAMPLE 1 toe/139119140 t,o 240 ,toform an alkylolamide, and thenmeactmg about a 2 to 1 molar ratio of pressure) was applied and thetemperature was The amidoesterof stearicncid,'ethanolammeand' :the al-l yl l an aliphatic ,dibasic acid dimerized linoleic acid :by heating said gsecondelnentionedreactants to i n 1 a i iabqut i 'np e hereaction A=mixtureof mole-10f dimerizedVlinoleicsacid' to ;1 mola ,31 ofdstyearicp acid with anamine and 1 mole of ethy'lol stearamide was heated at Selected. fl'olflhthg gloup co i ti ofumono and 0- 5 and 1 mm. "pressure until there ;:diethan o1a mines Joy-heating said reactantszto was no further evidence of the evolution of water -about 14010-240213. to form an a1kylolamide,.and ('about6 hours). The cooled productwas alight then reacting ab t a g at i mola'r'ra'tio the "bmwn, Semi-translucent'Waemelwa art-70115 4 15 ky olamideiwith an aliphatic dibasic {acid by 9 heating said second-mentioned reactants to about 180 to 240 C. to complete the reaction.

' 4. In a process for preparing an amidoester wax product from a saturated monobasic fatty acid containing an even number of carbon atoms within the range from to 26 carbon atoms, the step of reacting an alkylolamide formed from said fatty acids and an amine selected from the group consisting of mono and diethanolamines with an aliphatic dibasic acid in a 2 to 1 molar ratio by heating said reactants to about 180 to 240 C. to complete the reaction.

5. A product produced in accordance with the process set out in claim 1.

6. In a process for preheating an amidoester wax product, the steps of condensing about a 1 to 1 molar ratio of a saturated monobasic fatty acid containing an even number of carbon atoms withinthe range from 10 to 26 carbon atoms with an amine selected from the group consisting of mono or dialkanolamines containingat least 2 carbon atoms by heating said reactants to about 140 to 240 C. to'form an alkylolamide, condensing about a 1 to 1 molar ratio of said alkylolamide with an aliphatic dibasic acid to form a carboxyl compound by heating said reactants to about 140 to 240 C., and then condensing about a 2 to 1 molar ratio of said carboxyl compound with an amine selected from the group consisting of mono and dialkylanolamines containing at least 2 carbon atoms by heating said reactants to about 140 to 240 C. to form an amidoester wax product.

7. In a process for preparing an amidoester wax product, the steps of condensing about a 1 to 1 molar ratio of a saturated monobasic fatty acid containing an even number of carbon atoms within the range from 10 to 26 carbon atoms with an amine selected from the group consisting of mono and diethanolamines by heating said reactants to about 140 to 240 C. to form an alkylolamide, containing about a 1 to 1 molar ratio of said alkylolamide with an aliphatic dibasic acid to form a carboxyl compound by heating said reactants to about to 240 c.,

and then condensing about a 2 to 1 molar ratio of said carboxyl compound with an amine selected from the group consisting of mono or diethanolamines by heating said reactants to about 140 to 240 C. to form an amidoester wax product. v l

8. In a process for preparing an amidoester Wax product, the steps of condensing about a 1 to 1 molar ratio of stearic acid with an amine selected from the group consisting of mono and diethanolamines by heating said reactants to about 140 to 240 C. to form a alkylolamide, condensing about a 1 to 1 molar ratio of said alkylolamide with an aliphatic dibasic acid to form a carboxyl compound by heating said reactants to about 140 to 240 C., and then condensing about a 2 to 1 molar ratio of said carboxyl compound with an amine selected from the group consisting of mono and diethanolamines by heating said reactants to about 140 to 240 C. to form an amidoester wax product.

9. A product produced in accordance with the process set out in claim 6.

OTTO TURINSKY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date' 2,173,058 Kritchevsky Sept. 12, 1939 2,173,448 Katzman et al Sept. 19, 1939 2,334,852 Weisberg Nov. 23, 1943 2,356,408 Kelley Aug. 22, 1944 2,371,097 Cahn Mar. 6, 1945 2,388,281 Orelup Nov. 6, 1945 2,394,833 Young et al Feb. 12, 1946 2,410,788 Morgan et al Nov. 5, 1946 2,410,789 Morgan Nov. 5, 1946 2,441,063 Gilman 'May 4, 1948 2,449,926 Cohn Sept. 21, 1948

Claims (1)

1. IN A PROCESS FOR PREPARING AN AMIDOESTER WAX PRODUCT, THE STEPS OF CONDENSING ABOUT A 1 TO 1 MOLAR RATIO OF A SATURATED MONOBASIC FATTY ACID CONTAINING AN EVEN NUMBER OF CARBON ATOMS WITHIN THE RANGE FROM 10 TO 26 CARBON ATOMS WITH AN AMINE SELECTED FROM THE GROUP CONSISTING OF MONO AND DIALKANOLAMINES CONTAINING AT LEAST 2 CARBON ATOMS BY HEATING AND REACTANTS TO ABOUT 150 TO 250* C. TO FORM AN ALKYLOLAMIDE, AND THEN REACTING ABOUT A 2 TO 1 MOLAR RATIO OF THE ALKYLOLAMIDE WITH A ALIPHATIC DIBASIC ACID BY HEATING SAID SECOND-MENTIONED REACTANTS TO ABOUT 180 TO 250* C. TO COMPLETE THE REACTIONS.