Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR PREPAR~NG A~DES OF N~ YL POLYHYDROXYALKY~
A~ES
lS FTF~n OF 1H~.INrVEI~IION
The present l~lio~l relates to an i-~-~lu~d process for ~ 8 amides of
N-allyl polyllyd~o~y~llyl amines, ~Q~ret;~lly ones having good color and low levels of
undes.l ble by-products.
BACKGROUND OF lnl~ INV13NTION
The m~mlf~lre of N-alkyl polyllyd~u~y~Ltcyl a-m-ines ~N-alkyl polyl.ydrc,~y
amines), such a_ N-methylgl~ -r, and the fatty acid amides thereof, has been
known for many years, and such m~t~ le are ~ ~b'e CQ~ ;a11Y. Recently, there
ha been ocç~Q;~n to employ N-aLtcyl polyl-yd-u~y amines, e.g., in .r~ u~Q with, e.g.,
~tty scid esters to pl~pale fatty acid polyhydlu~ amide dcl~ nte for use
2s in rlDA~ ,R products. It has been ~etf - .~ d that care Jnust be taken in ~ N-
all~yl polyLy~l~osy amines and amides to provide the amides with the best color.The present i.l~l;on affords access to high quality polyhy-Lusy fatty acid
amide sud~ct~. The present U1~nliOn provides means for pl~&ing N-allyl
polyl-ydlu~y amine amides which are almost water white, esper~ y amides of N-
~ lL~ ur~ lle in higb yields, and more ~pe~slly, amides of N-methyl~1u~ e
co~ g low levels of cyclic m~tPri~ls as h~ closed
BACKGROUND ART
~ cose ledù~ Am;rl~tinn proces~es are tlicrlosed in U.S. Pat. No.
2,016,962, Flint et al., issued October 8, 1935.
3s U.S. Pat. No. 1,98S,424, Piggott, issued Dec. 25, 1934, r1i5AlOses
U~ 8 ~tex~le ~ by l~&CLi11,~ (a) the product of heating glucose and
a~1UeUUg m~h~1&I1IInC in p~..~.lce of hydrogen and a hydrogc ~ catalyst under
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ple..;,.ll~, with (b) an organic carboxylic acid such as stearic acid or oleic acid. The
conf~ cA~;nn product, prepalcd at about 160~C, is said to be Npredc~ y, if not
e,~,L~ ely, an amide" and is ass~.lcdly of the finrnAlllAA R-CO-NRl-CH2-(CHOH~4-CH20H wLP~in R is an allyl radical c~ g at least 3 carbon atoms, while Rl is
s hydrogen or an allyl radical.
U.S. Pat. No. 2,016,962, issued Oct. 8, 1935"licrloses a process for pl~u
glllcA...~ s and related products.
U.S. Pat. No. 2,703,798, ScLv~al4 issued March 8, 1955, asserts that
compositions produced by l~a_lh~B fatty acids or acid anhydrides with N-
10 alkylglll~-A~ s (p~,~ hly such as the process as taught by Piggott) have poorcolor and poor dete.~.-~ p-up~,.Lies. Thus, Scl-v~_~ teaches problems acsQc;stedwith fo~ g the crn~l~ncAtisn products of N-mcmnAlkyl~llrA~ Ps and fiatty acids,
with respect to unde~ ~le color ch~cle~ ;~l ;rC~ and dcL,.~n~ prop~ lies.
According to S-,l-w~4 a~plo~;~..AI- Iy equim~lAr l lu~JulliùlL of N-
lS mnnnAlkylglll~ . es can be reacted with fatty alkyl esters by heating at 140~C-230~
C, plef~ bly 160~C-180~C at normal, reduced or S~C Al~nS1~k-A-;C plC.~ S for a
period ~sol...i~l~ in excess of one hourN during which time two initially ;~ c--;ble
ph~ses merge to form a product said to be a useful dete.~,~l.
~llitable N mnncalkylgll~c~ es are ilh~ cd by N-methylg1-~c~ e, N-
ethylglllrAmirle~ N isoplo~ llrAmins and N-butylglllc-a-minP~ Sllit~ e fatty allyl
esters are illu~ ,d by the product of 1e&L~ , a C6-C30 fatty acid whLh an -lirhA~Lic
nhnl e.g., methyl ester of lauric acid.
More recent ploce~_s include those desr-;l~ed in U.S. Patents: 5,334,764,
Schi~Pl Connor"ehllm_tP~ and St. Laurent; 5,338,486, Cnnnnr, .erhP;1~pl~ and Kao;
2s 5,338,487, CQnnclr, !Srhe;1~Pl and Kao; and 5,380,892, Connor, Srh~o;bp1, and Kao, all
of said patents being l~c~olahd herein by lGr~ ce.
Accord;l.~ to Thomas Hedley ~ Co. Ltd. (now Procter ~ Gamble Ltd.), British
Pat. No. 809,060 p-~bli~h~d Feb. 18, 1959, the c~ .pc,~ c made by the process herein
are useful as ~--- r, ~ for laundry d~t~ ls such as those having granular form.
Hildreth (supra) ~ use of the cc--.l~o~ e herein in the blc-' -m;ctry field as
det~ agents for ~ hili7i~ plasma ~~ cs and EP-A 285,768, ~ l.r~
Dec. 10, 1988, d~ec.;1,rs apr~ ofthese co~ u~ as a !1~ 1. Thus, these
c~ -l-o~ , or co~--l-o~ n~ , them, can be highly des.._~le ~
Yet aao~ ,r process for making co---pGs~Lol s co--~ g the amide co---~ùuilds
35 of this ~ll.~.Lol~ is inrl lded in the ~o~ d ~ los ~- ~; of u~p~uv~d l~
See EP-A 285,768. See also H K~lLL ~ , Tenside ~c---r,~ D~lL~ g 25
(1988) 8-13, inter alia for e~rlitir~nA-l AicrloCllr~ of ~-uces~s for maldng N-
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a~1~ Jc~ Fs All of the above patents and publie~tionc are h~co~G~led herein by
~rtl~.,c~.
SUMMARY OF THE INVENIION
The present de~lop..le~ relates to a series of uul,lo~ ,.c.lls relating to
l,rocesscs for ~ palU~g amides of N-allyl PO1Y1~YdIUA~ amines ~N-sll~yl&l~lo
polyols). Both the N-allyl POIYII~tIOAY smines and the source of fstty acyl groups,
e.g., esters, used to foml the smides sre sele~led to have good color, the ~erl~tinn
co~ ;o~5 are sFI~cled to avoid the formAtinn of color ,.~ c snd pr~u~ for
color ~ .;A1c, and/or the smide product is treated with an ion e~ ~G resin,
10 ~I~Lw'cs of ion ~ ng~ resins, or cc ...h;.~AIiOnc thereo~, andlor a redur~ing "bleach"
to ~c~ , the best color amides. The CO~ 1 Q" of all of the Illly~ .l.e.lLs is
.~,quu~d in order to achieve amides with the very best color for f~ 3 d~,t~w~t
co..~o~ ~isnS~ especi~11y liquid dete~g~.lL comrositinn~ that are ~water white" and
which contain low levels of cyclic rnAt~Ale
lS The iu ;ol- provites a process for ~.ep&.. ~g polyl,~o~ tty acid amide
;,~.. r ,~ , c,o ~p i- ~ r ~ Lul~, a . . n l-"l sF1e~,~ed from the group co~ g of fatty
acids, fatty acid anhydrides and filtty acid esters, Psper;s1ly fatty acid esters, hs ling
greater t~an 98% hAn~ re at 460mn with an N-al~,ku,uuo polyol having a
Gardner Color of less than 1 (<0.1 abso,l,~lue at 440nm), e.g., methyl esters orhi~e~id-s. CrystA1l;7Ati~n of said N-a11~1&1luhlo polyol csn be used to provide the
ap~.~.plla~e pudty snd color. N-all ~ nu.o polyol vnth this Gardner Color is ~stable"
for three houas st 130~C. The N-aLI.~l&.uno polyol i_ C4'-8~ ,d stable if it has a
Gardner Color of 4, or les~, a~er three hours under these ~n 1:l;n~8 A less purc N-
all~ u~o polyol will be a dark brown afcer three hours under these Co~ ;o~8
2S Also, in o~der to ~ the be~t color amides, the d~ ~;on of N-all~12u.uno
polyol should be carried out at b~ en about 110~C and about 160~C for a period of
time of les_ than about three hours, more preferably at a l_.u~c.~u~, of from about
120~C to about 140~C for a pedod oftime of les~s than about one and a halfhours and
even more p,_fe.~bl" at a t~,.ll~al~f of from about 130~C to about 135~C for a
period of time of less than about one hour However, for co~ ~ f c;dl practice, good
results can be ob~ d with de~d~a~l times of from about four to about eight
hours, ~ bly from about five to about six hours, to t~,CC ~d~te CO~ c;al
e~l~ p~ mit~tion~ A more pure N-al~ U.O polyol can be achieved by
cryst~lli7~tion from an P~lleollC sol~ltion, either with, or without, an organic solvent
3S present
The deh~.t~l N-all~yl~l~ulo polyol is then rea~ted with, c.g, fatty acid esters
and ç~pecially l~ ce~ides~ to form fatty acid polyll~ Ar amide sur~ctants.
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The reS~lting polyLydlo~y fatty acid amide ~~ ct~nt is then post treated with
an ion ~ A~e resin, rï~ixture of ion e-~ ge resins, or CO~ ;On~ of ion
e resins, and/or reduçir(g bleach such as NaBH4, etc., or Ly~o~ ;nn over
a catalyst, as taught he.e~l~ler, and, optionally, co~ nc of ll~.a~ A
5 particularly c~ e post 1.~ is the hydro~en~tion of a sc~l~ti~-n of the
polyl,~d.u~y fatty acid aïnide s~ ot~nt over a hydrog~n~tin~ catalyst like nickel,
pS~n5~ m, copper cl--u-- ile, etc.
In a p.~ ,d process, the fatty acid ester is a Clû-Clg alkyl or alkenyl fatty
acid methyl ester, or, I~;~ly~,~,.ide, and the N-alh~,k,,--u.o polyol is sf~ cl from N-
0 methyl gl~lc~mine, N-methyl fmct~mine~ N-methyl In~lt~min~ and N-methyl glycerol
amine.
DETA~ED I)ESCR~PTION OF 1~ INVENTION
The p.uces3es of this invention employ s~le ~e i reactants, N-alk~l~-~.o polyolsand sources of fatty acyl groups, with good color, espe~i~lly color that is he&t stable.
lS The ~colorN .'.f~ d to herein is the Gardner Color, e.g., of the N-alkyl&.. no
PolyoL the N-alkyl&..-ino fatty acid amide, etc. NGardner Color" is the s~du~l
Gardner ~ ,.--~-L known in the art. A Gardner Color reading near zero
(sol~fion) ~ ,s_lt~ a nearly color1~c (Nw&ter-whiteN) s~ ti~n Gardner Colors
below about 1 are ~ u~cd for the N-allylarï~ino polyol re~ct~nts, and it is pl f~ d
20 to have Gardner Colors dose to 0.
Gardner Color is d~t~ ed by ~O.C.S. (~ e ~c~ Oil ChPmict~ Society)
Offlcial M~thod to la-64, entitled COLOR Gardner 1963 (Glass S ~ d~ds)
est~hlich~d 1978 and revised 1982. The e~ p--. -l and ~ d~ds for de~ --A~g
Ghrdner Color can be y~ d from Delta S~ntifi~, Box 5728, Long ~a~ New
2S York 20014, or from Gardner ~ lo-.~, Silver Spring, ~rylaD~ U.S.~ As used
herein, the Gardner Color limits typically refer to the color ~ from the color
bodie~ that are present, or which are the result of the de~ l,ed ~-1 ~tinns and not to
d~ ldy added color ~
The odor cl~ ~'e~s of the N-alk~l~u...o polyol ~~4 and it~ amide, are
30 s~ lly free of amine or "fish" type odor (once any exces~ N-alL;I~u.~u is ~,,ov~d) and also i,~,bs~ lly free oftypical bro. ~lU~ sugar odors.
~he N-alh~l&..uno Polyols
S ''e N-aLt ~,l~.uno polyols can be p~e,.~d by IJ-UC ~ C5 similar to those
dr~ -ed in COlJe~ld;1113 U. S. Patent Appli~tir~n Serial No. 07/907,382, filed July 8,
35 1992, in the name of Junan Kao et al. for PROCESS FOR PREPARlNG N-
ALKYLA~IES lN AQUEOUSIHYDROXY SOLV~TS, said ~ppl;c~ m being
~co.~o.~ed herein by .. f~.~lce, e~pe~lly page 6, line 4, to page 23, line 3 and
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EXAMPLES I - VL and IX - XIV. The pol~ .,y amine used to form the
polyl.~d.u~ acid amide can be made by any process that wiU provide the desired
colûr.
As ~ e~ he.~ n- ~, N-all yl~l~O polyols with good color are achic~.,d by
5 careful 5rle~ n of reaction cQ~.tl;,;c ~-c
The reaction for the ~le~alaLiûn of the N-alkylamino polyols (also le~.-C~ to
herein as "polyl-~Lw-y~-l"~es" or "N-alkyl polyl-~llo~ aminen) herein can be termed
the ~R-l~ re~cti~ n, and is illustrated by the for~n~tit~n of N-m~Ll.ylgl.~ min~, ~I.e~
Rl is methyl.
10 Adduct Process
In this f~rst v ~ ;QI~ of the R-l re~ctinn, the process involves pre-reacting the
amine and red~ g sugar to form an adduct.
water and/or organic solvent, e.g., ~ h~o
RlNH2 + glucose ~ Adduct + H20
The Adduct has the r, - ".. l~ (I) as foUows:
O
RlNH- ~- (CHOH)3 - CH- CH20H
catalyst
Adduct + H2 ~ RlNHCH2(C~O~)~lCH2OH
The ~e~,lA~, solvents and catalysts used in the R-l l~ rtion are all well-
known ...~f ~;~ tho ~gh not usually used in such ~ ied fonn for maldng
det~rg~.~t ~--- r ~ 3 and are available, at least in some form, from a variety of
CQ~ sources. The following are nn~ g . i'es of ~sterisle which can
2s be u~ed herein.
~ min~ M~ter~sJ - The '~N-aLt~ ~e~ used to form the N-aLIcylsmino polyols
include p-~y amines of the forrm~ls RlNH2, wl.~ Rl is, for . , 'e, aL~cyl,
e.g., Cl~1g, ~osre~slly Cl-C4 alkyl, or the co--- ~o~.~l;-.g l-ydnJ~.~ llcyls, e.g., Cl-
C411~ A~ . F - ~tor include methyl, ethyl, propyl, l~dr~ and the likc.30 No~ p examples of amines usefi~l herein include methyl amine, e~yl amine,
propyl amine, butyl amine, 2-l~ydr~ I'up~l amine, 2-L~Lo~y~ roy~ 2-
L~ l amine; l-..~ell.o~.ol ~1, and methyl amine. The C1~3 aL~l~.llncs arc
p.~-_d, and N- ~-~ e is most p ~f,.-~d. All such amines are jointly ~~
to herein as "N-alkyl amines." The amine can be either a~Luus or in a solvent,
3s e.g., s;~l~,c~ e solvent, of a CQ"C.. ~ ion offrom about 30~/ to about 90%")~fe. b3~,
from about 40% to about 70%.
Polyllydlo~y Matenal - A p~ ;lled source of pol~,L~droA~ m~t~n~le usefill in
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aU of the R-l re~ctionc co~ ,.;ce recl~lcin~ sugars or re~l~ring sugsr de~ivali~.cs. By
"sugars" herein is meant re~l~ring sugars such as glllcosP, fructose, ~ n~ se~ lactose,
m~ltose, xylose and the like. The term "sugars" herein also ine~ Pc glyceraldehyde.
Such "sugars" can include m~tPri~le which break down to form sugars, such as plant
syrups such as cane syrups, corn syrups, potato starchderived sugar syrups,
hydrolyzed wood pulp-derived sugars and the like. High ~uctose, high glucose andhigh m~ltose syrups are cc~ l and "1. r~ d, ~Cpecislly if their Gardner Color is
S~ticf~r,tQry. The l~kul~ sugar m~te,n~l COlll~li~S, for this first v~ristion, an adduct
with the amine such as ~ lh~l~luu-c. The species are clet~ -fd ( ~-e~-cd) by g.c.
0 analysis, (gas-liquid ~,lu~ graphy or "g.l.c.n) using Hewlett-Pach.. l 5890 Series 2
on column i~;e~l;on using DBl 15 meter 0.25 m film thickness n~ 250 m.
A particular alv~ c of the "Adduct" process is that the "Adduct" can be
formed in the p-~s~ince of water. Acco-dingly, raw m~teri~l$ such as corn syrup, and
the like, can be used as the sugar source. However, the sugar sol~ti~n can be
lS plcp~n,d from g-~u.,llar, powdered, etc., sugar by dissolving the sugar in the solvent,
prert.~bly ~q~eovs solvent. CO~c~ alions of sugar in the solvent, e.g., water, are
typically from about 40% to about 90%, p~,f~ly from about 50% to about 70%
(TypicaUy, 71% is the upper limit.) It is highly uu~oll~ that the color ofthe starting
sugar m~tf~ri~l, for plep~u.g, aU N-ah~l~-u--o polyols, be l~s than about one on the
20 Gardner Color scale, p.~,f~;~dl)ly less than about Gardner 0+, and more preferably
about water white. Typical color mgtP islQ that are present in the starting sug. r
mgt~riglQ neg,&L~ affect the catalyst . nd the .~Lon yield. The_e color ~
Iso co--' ~ ibule to the ~,~-lual color of the N-all~yl~.lu.o polyols. Such colors can be
le.~u.~, if present, by proce.l~ such a "carbon ble~ B " in which the color
2s msteri~lQ are adsorbed. The sugar ~gterjgl i_ p-~,f~, bly hsn~llP~d wi~lwul e heating and/or under non~ 3 contlitinnQ to prevent degradation.
Of course, use of sug. rs having low Gardner Colors (e.g., 0 or <1, i.e., water-white syrups) to forrn the N-. ILyla~lfu~O polyols will help ensure that N-, Lkyl~ o
polyols having desirably low Gardner Colors will be plù~ ced Stated otherwise, use
30 of low (~1) Gardner Color wgars (pl-,fe.ably white solids or water-white sohlti~nQ)
and use of the l_~ioll so~ -e ~liQrlosed herein results in low Gardner Color N-
alkyl~ulullo polyols.
~ stsl~yst - A variety of hydrog~c .~I;nn catalysts can be used in the R-l r~_Lon.
Tn-1~,ded among such catalysts are nickel (~ d when treated as ~
35 h~ller),pl ~ u ~,p~ m,iron,cobalt,l~ ,varioushydrogen~ti-nalloys,
and the lilce. The catalyst used in the hydrog~c ~ step is p~ r a p~ ,ul~e
nickel catalyst, Raney nickel, nickel, other nickel catalysts affi~ced to ~I,;.~ e
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m~tPri~lc such as silica or ~ min~ Catalysts which are easier to remove (e.g., by
filtration) are plc;r~lled. Highly prere led catalysts herein cc--~ e "United Catalyst
G49B,N HUnited Catalyst G96," and NUCI C46N particulate M catalysts supported onsilica, available from United Catalysts, Inc., Louisville, R~ u~L y, and Raney nickel
s type catalysts from W.R Grace & Co., of R~ltimore~ Maryland, such as R~4200 and
RA3 100.
Acll-c~ g good color also r~lu.l~,j o ~ 3 and 1llA;IIIil;n..~3 the activity of
the pl~f~.led nickel catalysts inrlutlin~ any of the cG,-~ ~I;nn~l Raney nickel or
~uppGlLed~ nickel catalysts well-known in the art. ConvPntinn~l nickel under thelo tra~len~rlr RAN~Y NICKEL 4200 and 3200 (Grace Chemicals) are quite suitable for
use herein. UCI (IJnited Catalyst, ~c.) G-96B and G49B and G49C are also
r ~ -~1c W-lth respect to the nickel catalyst, it is beli~d that ~llOV..1~5 oxides of
nickel from the catalyst ~r~ or ;--~l~edes ~ ~tl~tinn of nickel ions into the
r~;libn mitieu, and thus results in the rO----~ of l~aclioll products having a
lS dc~ bl~ low nickel cont~nt More~ r, it has been found that thc nickel catatyst pre-
treated and ~ ,f~,l~ly post-treated with p..~ Pd llydr~en can be re-used in
multiple ~bse~lv~ ~On~, thereby yielding a ~~I.s~ overall cost savings. In
general, nickel c..~ ;.4 such as those that are CQ ~ c;&lly available, typicalty are
co..~ ~ with, e.g., oxides of nickel, organic m~tPri~le, excess caustic, and/or
20 ~ min~ fines, P~rer-~lly after sh;~ ~ and storage. The nickel catalysts that are used
in the processes herein are pl~,f~ly free of catalytic activity ;~ 9 .~ s ofnickel oxides, organic m~teri~l~, caustic, ~lllmin~ fines, etc. Tlie.. rO.." it is dcs.- ~le
to wash the catatyst with one, or more, solvents to effect l~ Val of o.~ cs and/or
water-soluble m~tPn~l~, to preferably lower the p~ and/or treat the catalyst with a
25 strong r~J~,e;-~g agent, c.g., h~ g~n gas under high ~ , and/or t~ Lule
co~ , to destroy, or remove, the nickel oxides. Once the catalyst is "c~ nP~ "
the cataly~3t is d~ d under non-~ 3l,1s ~~, e.g., I~l .,gen gas,
or, more desirably, a leJ~ gas, e.g., hydrogen. Any ~ to the normal
.h-.e should desirably occur for 021ly short periods of time and while the
tc.lIp~ lun~ U lOW The activity of the catalyst can be incl~d ~ A~.l.Ally by the
re~lllctin~l, or removal, of these ;~ " ;1 ;p~A" even when they are present in very small
~ ,9~ The res~llting catalyst also provides amines, and ll-e.~,fc,l~ amides, with
good color.
~ When the nickel catalyst is in contact with either adduct or N-allyl
35 pol~ ~o~Ollyl amine, the h~Logcn plc~ should be ~--A;--~ F~ to r..~:... 7
catalyst ~ t-;l;~ n ~ rly~ ahigh hydrogen pl~ e.g~, from about 100 psig
to about 3500 psig, ~ f~ably from about 500 psig to about 1500 psig, and a
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t~ c.~Lu~e of from about 20~C to about 135~C, y~ere~ y from about 40~C to
about 85~C, wiU reduce the level of nickel ion dissolved in the N-alkyl
polyl-~ uAy~lkyl amine, and, by depositing the nickel back onto the catalyst,
l~e.~e.~le its activity
s A co ~ of hydrogen gas and s~ cled p.~ .. pe.~lui~ cnnrtitinnS
can reduce this ~ hiti7~tion and, in fact, reverse the process to deposit nickel and
eg_nc.~e the catalyst Low~ g the soluble Ni content in the N-aLkyl POIYIIYdIOA~
amine product to less than about 10 ppm, prertl~bly less than about 5 ppm, more
preferably less than about 2 ppm, wiU cfIt-;L~ l~.,n~ ~Le the catalyst.
0 When the catalyst is sepal~l.,d from the N-alkyl polyll~d~ûAy~Ucyl amine, the
t~.llp~ila~ul~ should be less than about 135~C, pler~ bly less than about 85~C, and the
separation, typicaUy filtration, should be ~cco~ ed under hydrogen pl~
Regen~.alion of catalyst can be achieved using the ~tep d~CC ;l ed for initial
activation
lS The N-aLyl.Y---no polyol .~_~-L herein, which is "~ y free of nickel",
cc~ c no more than about 20 parts per m~llion (ppm) nickel, and pr~,f~.~ly less
than about S ppm nickel (Ni~). Nlckel can be CG--~.~ll~ llle~d by
C~ .I;nn~l atomic ~bsolylioll s~ Jscoy~ using diluted samples (5/1 dilution to
tlL.~ce).
Solvent - FG~ ofthe adduct in the R-l process is co-~ ntly camed out
in water and/or orgsnic solvent, ecpec~ y polar, most p~ r L~d~u~y _olvents.
Typical; ~ 'e9 of organic solventc useful herein in the fc~rm9tinn of the &l~ulle-~~lgar
adduct include ...~,l1.AI101 (plertll d), eth9nnl, l-plUpanOl, iSO-plUp&l~Ol, the butAnc~
lel~e glycol, 1,2-propylene glycol (~lerN~,d), 1,3-propylene glycol, gly~,~ul and
2s the lilce The amine itself can also r.~ as a solvent, typically at mole ratios of
A.~.;..P, ~p,.Ar offrom about 4:1 to about 30:1
The hydrcg, ~AI;n~ reaction of the R-l I~Lon can also be carried ûut in the
pl~o~CP ûf an organic or aqueous solvent which dissolves the adduct
HydrogPnAtinn solvents are, cGl-~iellLlr, polar, P~pe~sl1y l-~L~Ay, solvents, i e, of
30 t_e same type as those m~ntiQn~d above for use in the fiCl~9tic~n of the adduct. When
S~ A11Y al~d-uu~ organic solvent is used, the umc~cLcd amine is ~-,..,o._d with
the water after the adduct ~ step. However, when an P~ e solvent is
used, the amine and solvent are not ~.nuv~id until the catalyst r~,~o~ step.
Water is the p.~,r~ ,d solvent for the l.~rlLo~ reaction l~th~nnl is a
3s pr~ ,d organic solvent for use in the hydrogen-s-~Qn l~lion.
General R-l Reaction Col~dilions - R~(Ctinn CQ.~ ;nl-~ for the R-l
reaction are as follows. Step (a) - Adduct fo-l--alion - Step (a) of the process is
CA 02223981 1997-12-05
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_ g _
~l~fc.ably carried out at a t~n~ e of from about 0~C to about 80~C, l,r~ bly
from sbout 10~C to about 60~C, for processes l~titi~r~g organic hr~U~y solvent and
below about 70~C, ~ bly less than about 50~C, more plef~d~bly less thsn about
30~C, more prtrel~bly from about 15~C to about 25~C, for ~queol~s solvents.
s The reaction time uset for adduct fc~ will typically be on the order of
from a few ...~.-"~,s to about 20 hours, ~epen~;uB son~ al on the reaction
le...l)e.alul~; chosen and/or the ratio of amtne to sugar. In general, for the organic
solvent, lower lea~;l;oil te..lpe.~ s in the range of 0~C-80~C require longer reaction
times, and vic~.~. In general, for the organic solvent, over a l)refe.r~d 10~C-60~C
1G&~;LiO11 t~ C.aLui~, range, good adduct yields, e.g., more than about 90%,
prufe-~bly more than about 95%, are a~ e1 in 1-10 hours for the organic solvent.For the lower reaction le.l~y~.alul~ range, 0-70~C, pl~,f~ly 0-30~C, that gives good
color, especially in water, the r~ ti~n time can also be as nwch as 10 hours, but,
typically, eq~ ;hrillm is ~b~ Y reached within about four hours or less,
IS especislly with higher n-~ r;~--gPr ratios. The t~ p~.~lur~ and reaction time are
s~lected to give an adduct with a Gardner Color of pr~r~bly less than about 1.
Good adduct color is "~C~-~ r for OblA l~ B good l a tions and color in any
~I ~S~ dlu~f I~'liOIl and ~ ~ catalyst activity. Below a
Gardner Color of about 1, the res~lting N-allyl polyl.y~ r arnine, and c.~ e~ ently
the resulting amide, has good color. The color bodies can bc ~ d by, e.g.,
carbon bl: & -hi~ as used for the sugar SQIUtiOn
The adduct also has a very low level of glucose. The glucose leveL as a
p~ of the adduct is pler~ bly less than about 1%, and more prl fe.~bly less
than about OIlC ~lf of one percent. fflucose i~ ,.es with the L~Lu~u~ I- &_lion
2s step to form the N-allyl polyllrJl~.Ar armine. Excess a2nine can also help reduce the
glu~ose level and ~--:--:-~ e rc~ of sorbitol during h~,~ug~ I~AI;OI~
In general, the t~nlJ~aLw~ will rise during adduct fo~ ~---I;on since the l~&_Lon
t-~,nic. Th~erore"~ g te.-~pc.alu-~s below about 3û~C, as l~.luh~,d in
batch p~ùce~ , involves providing cooling for the ~ nte and/or the l~.;liOn rnix.
T~l~ u~s above about 50~C require l~~_Lion times of less than about 10 ~ 5
to avoid ~ce~&~e color ro-.--AIi~ Such short times are normally not feasible except
in a CQ~ vO~iS l.a.~l;ol~ Even with such a co l;~ u-J~ reaction, back-rnLcing should
be ".:l-: ": ~A, e.g., by use of plug flow con-litinne~ to avoid ~ , e-l~o~ of the
adduct to higher t~--p~uies. Ide Llly, the adduct is p.u..l~ reacted with L~og~,n
3s to fo~m the c~ .on-~ 3 N-allyl POIYII~ UAY amine to ~ , degra~l~tion
Hûwever, le.~lp~ lul~ below about 30~C, ~l~f~.~bly Iess than about 20~C, allow one
to handle and/or store the adduct for at least several hours, which fA~litAt~s the use
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- 10-
of batch processes. At 0~C, the adduct is stable for 24 hours.
Surface l-~ e.aL~s~ e.g., when pr~h~ g the adduct for the hydrogen
reaction process, should be .~ ed below about 100~C, pref~.dbly below about
70~C.
S pcf~ nt con~ ons can vary. Molar ratios of ~ ne s~ r not greater
than about 7:1 are pr~r~ bly used herein, ~lthou~h ratios up to about 30:1 can be
used when the amine is used as a solvent, at least in part. Generally the desired
adduct form~tirm is achieved at a mole ratio of ~mine~ g~r vith an excess of arnine,
e.g., mole ratios of >1:1, prtr~.~ly greater thsn about 1.1:1, snd the lil~e, e.g.,
0 greater than about 1.3 :1. Typical ~a~ l~lL concf~ lions in the water and/or h~/dlUA~
solvent are in the 10-80%, typically 40-50% (wt.) range. Adduct forrn~tinn can be
carried out at ~I---n~h- ~ ;c or s~t.~ osl)h~cpl~ s.
Step (b) Reaction with Hydrogen - Step (b) should be nrC~ plicl~e~ so as to
avoid the prolo~ exposure of the adduct to the catalyst when the hydrogen
5 pre.,~ r~, is less than about 500 psig, and prl r~ly the L~dluge.~ p-.,~e should be
at least about 1000, and more pref._.ably at least sbout 1500 psig. K~eping this time
below about one hour, and pref;~ below about a half hour, ~ s the amount
of catalyst metal, e.g., nickeL that is Coll~_.Led to water soluble ion. Such ions are
unde~ ~le for a variety of ressons ir~ ing their affectt on color rc~ l;nn
20 ;~ o~ with other ~ t ~ ;~1~, ssfety, etc.
Step (b) can be carried out in either a slurry process or a fixed bed. Step (b) is
pl~ abl~, carried out at a te.~ of from about 20~C to about 120~C,
pl~t ably from about 50~C to about 100~C for organic hyJ~uAy solvent plOC~iC5
Step (b) is p.~vf~_bly carried out in two stages for nqueolls solver~ pluc~s~s The
2s first stage is at a ttvpc~lu r that is low enough to avoid ru~,i,.,- of the
c~ -ol~ti~g reduced sugar, e.g., sorbitol in the case of glllcosP, and other
ed l"~-u-lucts. Typically this is from about 20~C to about 70~C, more
,,.,f~ly from about 40~C to about 65~C, and even more preferably from about
50~C to about 60~C. ~ the second stage, a~er the rfv ~ (hydrcg~ AI;.~I~) of the
adduct to the N-alkyl poly}l~ LuAy amine is at least about 80% r~ -, ' 'e prtvfv.~ly at
least about 90% co~ i kle more p~lLrv~ at least about 95% ~ , the
le.l-pe.alule is raised to at least about 75~C, plefe ably at least about 80~C, and up to
about 135~C, p.lvfv.a~l~ 130~C, so that the le---~ adduct and any other m~qten~le
that may form color bodies are .--;-~ d and the adduct is at least about 95%,
pr~f,rv.~ly at least about 98%, more prtvfv.~bly at least about 99.9~/ co~v.l~d to the
co .~on&~g N~ cyl amino polyol. T}li8 second ~tage is r~Q .~ to the pr~&~lion
of N-aL~cyl polyhydoxy amine with good stable color upon l-P~ing Heat stability is
CA 02223981 1997-12-05
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,ro~cd for the N-alkyla~ o polyol by using excess amine in the prep~a~ion step
and a higher te.llpe.aLI~l~ at the heat l,eA~ step.
During Step (b) it is highly pl~f~.l.d to avoid loc~li7ed o~.-l-e~ e.g., at
the surface of the heating flr-~ or heat ~ clle.~r. Such surface or "skinH
s telllp ~alw~s should be below about 180~C, p-~ f~bly below about 100~C, snd even
more ~ f~ably less than about 70~C, during the first stage and less than about 100~C
during the second stage.
The reaction with hydrogen is prefe.ably carried out with limited initial water
when the solvent is an organic h~l~u~ solvent, ~tthou~h even then, water (e.g., up to
1:1 wt. H2O-~I~ohnl) can be present. Optional water removat from the adduct
pr~àl~t in Step (a) can be f ~. I~d by use of drying agents, or by simply i.L.;ppin3
water and sohrent from the adduct, and then .~ solving the adduct in fresh water-
free solvent. The 1.~ reaction can typically be mn, for; 'e, at
t~npc~a~w~ of 20~C-120~C at 50-1,000 psi or, for . . '- at 50~C-90~C at 100-
500 psi for periods of 0.1-3S hours, generatty 0.~-8 hours, typicatly 1-3 hours when
the organic solvent is used.
When the solvent co~ c water, the hydrog~ ;n~ r~ Lon is done in t vo
stages as .]~- ssed before.
The adduct/solvent se' l~isn used in the L~.Log~ reaction is typically at a 10-
80%, typically 40-50%, (wt.) solute level.
It will be &~cd that the s~ l;n" of l.~ ,xcll l~Lol~ cQn~litinnc will
depend so~ ...hdl on the type of pl~we e~ - to the fc" .~ or, so
the above-noted r~lion CO~ 5 can be varied without dep~L,.~ from this
i,l~..l~ion. However, as noted before, the hy~ e.l pres;,~e pl~f~ly should be
2s above about 500, p~ubly 1000, more pref~.ably about 1500, psig when the adduct
and the catalyst, e~re~lly the plefe.ret nickel catalyst, are both present. Use of
lower ~,r~ down to about 100 psig will require either a s~A-~e step to remove
M ion, or more prolons~ed post lr~ n~ as ~I;c,~55/~ hc.~ --An- r, to whieve verylow Nl CQnt~nt
IIy~oge~ reaction catalyst levels are typically from about 1% to about 100%,
preferably fronn about 2% ~referably about 5%) to about 30% ~lef~ably 20%)
more p.ef~bly from about 5% (~ re-~bly 10%) to about 15% (p.~ft;r~ly about
20%) solids by weight, c~ t~od based on wt. catalyst:wt. reduç;rg sugar
Step (c) F;~ g - The catalyst is then sep6l~let from the product a~er the
iOl~ is completed. The catalyst is l~llu~cd from the product of Step (c) which is
then pr~f~bly dried by cryst~ 7~tinn or by solvent/water i,~ ,pihLg, or by means of
,
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L~ dry-ing agents. This helps prevent reversion to the sugar starting m~tPri5~1
Step (c), when it involves solvent/water stripping, is preferably done in a wiped
film c~a~o~tor.
Steps (a)-(c) of the R-l process are preferably con~1ctecl under non-oYi~li7i-~gs contliti~nc (e.g., H2 or inert gas) to provide good color. Catalyst removal in the Step
(c) process is done plerelably under hydrogen plCSa~llc; to prevent M (catalyst)tliccQ1l1tion or at least under inert con-litionc
~lucose Addition Process
Another suitable process for plepa,il,g the POlY~ OAY amine utilizes glucose
0 a(ldition (The n(~ cose .A~ itionn process) after p~ g the catalyst and amine in a
simplified reaction which can achieve good results so long as the glucose is added
under a hydrogen plei.~e of at least about lO0 psig, l,l.,r~ bly at least about 500
psig, and more pief~,.~ly at least about lO00 psig, at a tc.~ .atul~, of less than about
80~C, pr~r~lr less than about 70~C, most ~lef~l~ less than about 60~C. The
lS m~tPri~lc and the cc~nAitiQnQ for the l~ ;"d- r of the rcacliol~ are the same as ~let~i1Pd
above for the adduct process.
The pr~alaLon of the N-allylaminol polyols by either of the processes can be
cQn-lucted in any well-stirred pl~.S;.~, vessel suitable for c~nr~1cting l-
~
rP~it~ne In a ~ll~e.~e.l~ mode, for the "t~T1~cose ~ titionn process a ~ ,S;,ul~,20 reactor ~-vith a s~,p~ate storage ft,S_.vulliS employed. The l~e3~ 0i~ (which, itseLfi
can be p~ Pd) c~ cA~cs with the reactor via suitable pipes, or the like. In
use, a stirred slur~y of the nickel catalyst is first nr1e-AnPA,n ;",~1 ~d:-~ being treated
with l-~dlu~en to remove traces of nickel oxides. This can be CC,~ ntly done in
the reactor. (~1l-, "Al;~L~ly, if the i-~A....rA~jl..~. has access to an oxide-free source of
25 nickel catalyst, ~ 1 with H2 is ~ eCe ~ . However, for most
mAm1fiA~lnng p~oc~es some trace of oxides will iç~i~ly be present, so the H2
r -1 iS p~efe-l~d.) Mer removal of excess slurry ..~r~A;.~... (water) the N-alkyl
amLne is introduced into the reactor. Thc.c~lc[, the sugar is introduced from the
storage l~Oi. into the reactor either under h~g~l pf ~ u~ or by means of a
30 high p.~c ~ p:-~g system, and the lea~iol~ is allowed to plocecd. The progress
of the l_Lon can be rn-~-- lor~d by perioAirAlly l~llU~inp, ~ '9 of the r~lion
ll~ule and analyzing for ull~ cled sugar using gas cl~u..~AIography (~g.c."), or by
heating the sarnple to about lO0~C for 30-60 r - ~ r s in a sealed vial to check for
co1Or stability. Typically, for a reaction of about 8 liters (ca. 2 gallons) size the initial
stage (to 95% of reducibles being d~ ed) l~ Ul~S about 60 .. : ~ , de~ 8
sOlll~,..l.al on catalyst level and t~ lp~.~lure. The le.llpe.alule ofthe reaction mixture
can then be raised to , ' the reaction (to 99.9% of the ~ b'~ being
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- 13 -
d~p'cted).
Cryst~ 7ation of Polyl,ydru~y~ f-s
The color quality, ~labil;Ly, and/or purity of the N-alkylamino polyol can be
further i~lp~u~d by a process of cryst~l1i7~tion of the N-alkyl~,....o polyol from an
s aqueov~ sol~ltion or water/organic solvent l,~Lulc. Cryst~11i7~tion is carried out by
cooling the aqueous n~ul~ of the N-alkylamino polyol from Step (b) to 0-10~C, ormore, preferably by col~ç~ Lillg the a~lucuus llli~lUI~; to about 70% solids prior to
cooling, and most ~ r~.dSly by adding from about 10 to about 200 parts of an
organic solven~, e.g., ~nf ll.~nol ~ceton~o., etc. either to the aqueous feed sol~ltion, or,
0 most plerc.ably, to the co~c~ aled sQl~ltion Highly pure crystals of the N-
alkyl~l-illo polyol form which can be ;CQ1~ted from the S-~P~ .I sol~tion by
filtration and/or CPnt~ifilg~tion To obtain the purest crystals ~o~ lc, the filter cake,
or c~ ;r.-g~ cake, should be washed with from about 0.25 to about 1.25 parts of
chilled (0-5~C) solvent. The wet cake can then be employed to produce polyl.y-llu~y
5 f~Ltb acid amides with ~ ~ccd color. The crys~lli7~ti~n method provides a
;,~ll~li~lgl~r illl~.ro.~ amide product.
F~----alion of Polyl-y~l-u~y Fatty Acid Amides
The N-al~ o polyol co- ~ u~ Ae ~.~,p~cd by either of the above l.~.~ l;n~
and having the rc~ui-. d Gardner Color can be used in an overall process for p~ii~g
20 polyl-ydru~ fatty acid amide s~ r~ which inrl~ld~C an amide-rt~ g reaction
co...~ reac~ a source of fatty acyl groups such as fatty acids, fatty acid
anhydrides and fatty acid esters, especially fatty acid esters, having greater than 98%
~ at 460nm with an N-alL~ no polyol having a Gardner Color of less
than 1 (<0.1 abs. at 440nm), more p ru~ bly esters which have been ~ictilled in the
25 p.es~ ce of from about 0.05% to about 2% alkali metal oxide, e.g., those pr~&~;d in
the rur.,go~ manner, in an organic hydruAy solvent in the ple3~Ce of base catalyst.
The fc-tnntinn of such s~r~ ! with high purity and low color is an espe~;slly
be~- r~e ~1 result of such a process when an organic ~ ~UA.Y solvent is used, since the
det~,~.l fnnnlllstor can pump and/or incG.~û.ale the poly~-~dru~ fatty acid amide
30 ler~tinn product plus the ~~_Lion solvent such as 1,2-1,r~p&l~e diol, (propylene
glycol), glycerol, or alcohol (e.g., in liquid d~le.~ ) directly into the final de~e~genl
forrmll~tinn This offers eco~ c advantages in that a inal solvent ~ nuval step is
rendered ~ c~ ,c .y, particularly where u~hol-s glycols or ethanol are used.
~ The polyl.~o~u-~-e products of either of the aforesaid R-l rea~ionc~
3s p.~,ft; ~bly with water ;,-~l,st~n;~lly re.no~cd, can be ~rther employed in an amide-
rO~ g reaction which is ~e~ ted herein as the HR-2" reaction. A typical R-2
amide-fo. ~ ~ :tinn herein can be illu~llaLCd as follows:
CA 02223981 1997-12-05
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-14-
R2COOMe + R3N(H)cH2(cBHaoseH)c~atca~y2sto~ eH,g.~ ;d~
R2C(o)N(R3)CH2(CHoH~4CH20H + MeOH
S wLer_.n each R2 is Clo-C20 allyl and each R3 is Cl-C4 allyl, Cl-C4 alkoxyallcyl, or
h~dr~ lkyl group.
Thus, the process herein can ~nco~ s an overall process for p~ ~u~g
polyl-~dlo~ fatty acid amide S~r~ option~lly c4"~r~;C~g an R-1 process as
dc 5~ d above and then r~_lu,~ the polyl.r.lluA~une having a color of less than
0 Gardner 1 vith a fatty acid ester having at least 98% ll~c-~ ce at 460Dm in an
organic Lydlu~.y solvent (pl~,fe.~bly, .~.CII.An~l) in the pl~,sc~ce of a base catalyst to
fo~n the polyl,yd.oAy fatty acid amide - ~- r~ l~..l (at a ten,~ u~ of from about
40~C to about 135~C for a time of less than about three hours, more pl~f~,.~ly at a
c.,l?c,.~Lule of from about 40~C to about 100~C, and even more plcfe.~l~ at a
tc.~lp~,.aLule offrom about 50~C to about 80~C for a time of less than about 2 hours,);
and optionally, l~OVUU2 said solvent. The rPclllting amide pi~du.l is treated with ion
~ ch~ ,e resin, more plefe.~bl)r a ~lule of acid and base resins, or, optionally, with
~J~ g bleach to provide a pro.lu~l that is r ~ lly "water white~.
In a more l"~.f~-ed ernhodi n~nt, the amidc ~ rt~nt is treated first with acid
ion e ~ resin to convert any soap to fatty acid and remove any residual amine
that has not been uj"~s,.led to amide. Then thc amide ~ is treated with base
ion e-~ g~ resin to remove the fatty acid. Both resin_ remove part of any color
bodies that have already fnrrn~d
R-2, or the co...l~ inn of R-l and R-2 leP.~ 8 herein, can be used to
25 prep~ polyllyd~uA~ fatty acid amide ,,...1;.~ ofthe 1~ (Il) as follows:
R2 C(O) - N~ ) _ Z
~1,~,.~.: each R1 is ~ Cl-C4 L~d-oc&~ L cl-c4 alkoxyalkyl, or h~uA~,Lkyl, e.g.,
2-Ly~lluA~ l, 2-}~LuA~ o~yl, etc., p-~ ..ably Cl-C4 alkyl, more preferably Cl orC2 allcyl, most pr~ Cl alkyl (i.e., methyl) or ~ LhOAY~ICYI; and R2 i_ a Cs-C3 130 L~oc~l moiety, p..,~.dljl~ straight chain C7-Clg atkyl or alkenyl, more
pr~,fe.~l~ straight chsin Cg-C17 aLIcyl or alkenyl, most p efe.~bly straight chsin Cl 1-
C17 aLkyl or alkenyl, or ~1 Alu~ thereof, and Z is a polyl,~Lu.~ d uc& l,yl moiety
having a linear l",Lu~ chain with at lesst 3 l.~LuA~L directly co~ d to the
chsin, or an allwA~ d~i~raLi~e (p~ bly ~lhUA~/htCd or pr~po~la~ed) thereof.
35 Z l,.ef~ will be derived from a 5~d~1C;'~g sugsr in a reductive pmi-~tion re&Lioll;
more preferably Z is a glycityl moiety. Z p-~f~l~ will be ~-'xted from the group crl~ g of -CH2~CHOH)n-CH20H, -C~CH20H) (CHOH)n-CH20H, CH2-
-
CA 02223981 1997-12-OS
WO 96/40619 PCTAJS96/07124
- 15-
(CHOH)2(CHO~)(CHOH)-CH20X where n is an integer from 3 to 5, .i.cl~ , and
R' is H or a cyclic mono- or poly- 5~rçh~n~t~, and alkc,~l&l~l d~ aLi~3 thereof.Most pr~,~wl~d are glycityls wh~ n is 4, particularly -CH2-(CHOH~4-CH20.
Mi~lwe., ofthe above Z moiefiçs are de~
s In Formula (II), Rl can be, for F~ r~ N-methyl, N-ethyl, N-propyl, N-
isop.u~L N-butyl, N-isobutyl, N_2 1~Yd-UAYeLI~YI~ N-1-n1~LLUAY1I1U~ or N-2-
h,~.ll OAY~I U~
R2-CO-N< can be, for ~ , co.- do~ ~I~,f.de, oleamide, lauramide,
dl" carn~sn~ t-~ .;de, tallowamide, etc.
Z can be l-de~A~lucityl, 2-deuAy~u~,~i yl, l-deo~y.l~ltityl, l-deu~la_Lilyl, 1-
deoxygalactityl, l-deu~yll~m,Lyl, l-deu~ to~riotityl, etc.
The following ~ , catalysts and solvents can coll~ueilLly be used in the
R-2 reaction herein, and are listed only by way of e~mpl;fi~ ~tion and not by way of
lim;tPtirn Such m~t~ are all well known and are luul;nely available from a
lS variety of co~ c- ~,ial sources.
~e~.c~ ls - Various fatty esters can be used in the R-2 r~ inrl~ g
mono-, di- and t~i-esters (i.e., ll;~c~,.;des). Methyl esters, ethyl esters, and the l~ce
are all quite s~ '~ The pOlyllyd~uA~ l~lllc Ic~ include re~ct~ntc available
~om the above-dr~ ;l,cd R-1 rea~;lion, such as N-alkyl and N-L~druAy~llyl
pol~ .lluAyal,.in~s with the N ~ b~l;luent group such as CH3-, C2Hs-, C3H7-,
HOCH2CH2-, snd the li1ce. ~POIYIIYdIOA~ UI~eS available from the R-l reaction are
plefc~ not GQ"IA~ Ied by the pl~3e.nce of residual z---u-~--l, of metallo
hydrog~n~tion catalysts, ~lthm~gh a few parts per million te.g., 10-20 ppm] can be
present.) Mi~ of the ester and I~uAlurt s of the polyl,~ d~ ~lul~e re~ csn
2s also be used.
Ca~ s - The cstslysts used in the R-2 le~-tinn are basic m~t~ tc such as the
~lL...;f~ d), hydro ndes (less prefe.l~d due to poCQ;~1e hydrolysis re~innc)~
C~~ t~'~, and the like. ~f~lt;d ~ Yi~le catalysts include the alkali metal Cl-C4~llrnY~1es such as sodium m~hsYirle~ pol~ u~;~c, and the l;ke. The catalysts
30 can be ~ d sepd~lel~ from the leclion nu~ , or can be gell~.al~d in situ
using an alkali metal such as so~illm For in situ ge.l~.~Lon, e.g., sodium metal in the
nl solvent, it is p-efe.lcd that the other 1~ ntc not be present until catalyst
g~~ lionis complete. The catalyst typically is used at a level of about 5-8 mole %
- ofthe ester react~nt Mi,-lul~s of catalysts can also be used.
3s Solvents -The organic }-,~dlUA,~r solvents used in the R-2 reaction in~ .o, for
exa~ple""f ~l~Anol ~thAnnl ~lop~lol, iso-~,lo~allol, the I~IA~nl~ glycerol, 1,2-propylene glycol, 1,3-propylene glycol, and the l~ce. luPll~Al~nl iS 8 pl~f~ f~ d alcohol
CA 02223981 1997-12-05
W O 96/40619 PCTAJS96/07124
solvent and 1,2-propylene glycol is a ~ r d diol solvent. Mixtures of solvents can
also be used.
General R-2 Reaction Conditions - It is also an optional objective herein to
prepare the desired pro.lucLs while .~ the formAtinn of ~;y~ d by-products,
~ ~ ~ OH
s e.g., OH OH
ester amides and color bodies. ~acti~n tc.~ Ul.,S bdow about 135~C, typically
in the range offrom about 40~C to about 100~C, pfCf~..~;l~50~C to 80~C, are used to
achieve this objective, esret~;Ally in batch p,ucesscs where reaction times are typically
on the order of about 0.5-2 hours, or even up to 6 hours. SG11~_~l1al higher
0 telll~Lulf s can be tolerated in cG~ vv!~ procf sse~, where reQ;~lf~n~e times can be
shorter.
Plllificn~iol~ ofthe POIYl-Yd.UAY Fattv Acid Amide
The POIYI1~d~A~r fatty acid amide ~~fiA~Ant p~epa~ d by the p~uce~s herein is
very pure and has good color. However, for products that are not colored, or which
5 are clear, even purer, less colored S~ tAntS are "~ L~. Acco,d,n~, the
PO1Y1~Y~OA~ fatty acid amide S~rfActAnt iS p,ef~.~bly post treated with an ion
AI~gf. resin, ~lliAIUl~ of ion ~ -nllAI~gf resins, or c~ ;on~ of ion f .~
resins, and/or ~ ~luc: ~5 bleach such as NaBH4, etc., or hydrog~nAti~ n over a catalyst.
Tlf nl--.-~nl with ion e-~ ,f resins can be very e~t~ ., if the ~ II. n~ iS
20 c~efully carried out. Since the minor CO--~ present are both cationic innature, e.g., amines, and/or anionic in nature, e.g., soaps and/or fatty acids, it is
desirable to treat with both anionic and rAAtit~nic (~cidic and basic) ion e-~ ge
resins. A p_lL-,uLu~ is to treat a s~ ti~-n ofthe polyl,yLuAy fattyacid amide ~fActAnt first with acid ion P~ ge resin to remove the amine and
2s convert any fatty acid soap to fatty acid and then treat with base ion ~ ,e resin to
remove the fatty acid.
Another particularly ~cli~-, post h l is the hydrogf~nAtion of a sol~tinn
of the polyl,yd,oAy fatty acid amide s-~ II over a hydrog~n-otinn catalyst like
nickel, pollo~ n~, copper cl~o" ile, etc. Su~ gly, the l~yLog~-~AI;o~ is c ~c~ in
30 el;~ n~ g color bodies and color body p~ ,U~ will~ou~ ad~ ely A l;~ g the
structure ofthe sl-rfoctont
The hydro~en-o-tinn is typically carried out in a batch reactor. A catalyst,
typic. lly of either nickel or pollo~ m is sluITied in a s -l-ltinn of the polyl,yLuAy fatty
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.
- 17-
acid amide s~ ct~nt and reacted under c~ n~itinns that will achieve the desired
i,n~ cm~;llL. Typical reaction con~litiQn~ are h~Lu~e.l ~r~l~; of from about 150to about 1000, pr~lably from about 300 to about 500, psi; tC..~ alu~t; of from
about 50 to about 120, p~f~ably from about 50 to about 65, ~C, to limit pole.lhal
s soap r~ iOn; and reaction time of from about one to about four, p.cr~.ably from
about one 1:o about two hours.
The color ofthe ~ r~ -.l is ~nea;~ as % ~ A.~ on at 420 n~nnl..tt~
against a 50/50 ll~ We, by weight, of .--~ ll.A~ tilled water blank. The ~ t~nt
is diluted to ~0% by weight with the blank solllt;nn and read in a ;.~echvphoto,n~ te~ .
0 Typical color of cn---~ ,;al prodllction varies from about 55% to about 70%
h~ n, as .-lea~d above. For clear products, the .-- n;.. , L~ cc;~
should be at least about 70%.
The catalyst loading to achieve 70% h~ epen~ on the type of
catalyst used, and the desired level of color .,ll~rovG,lle.~l. For nickel catalysts, the
15 loading ranges from about 2% to about 10%"~r~rel~ from about 2% to about 5%,
c,~lesse~ as weight of catalyst based upon the n~ t~nt in sol~ltinn These levels of
catalyst will raise the hl-n~ n from about 40%-48% to about 70% with 2%
catalyst and to about 80-85% with 10% catalyst. Post L~LO~t-~ I;nn with p~ m
catalyst produces ~lrPrjt~r color with less catalyst. P~1lAt~ m catalyst usage ranges
20 from about 0.005% to about 0.15% with r~ 8 h~n~ of from about 85%
to about 90% when starting with colors having IIA-~ nC of about 60%. For
c,q"~,p~. ;er~l~, a ~ nn of sbout 42% was raised to about 75% by nickel catalystand to about 93% by p~ ilm catalyst, using con~lil;n~c of about 120~C and about
360 psi hydrogen.
Another optinn~l reductive bl~c'i~ step utilizes a reduring m~tPri~l such as;
NaBH4, LiAI~, etc. It has been found that the pH should be from about 10 to about
10.9, pl~f~ably from about 10.1 to about 10.6, more pl~f~l~ about 10.4. This pH
range ~,lo~,ides ~ycellpnt bl~ ~hi~ at a good rate wilLuu~ ~ces~, creation of fatty
acid soap by hydrolysis of the amide.
The following . ~ S are intPnrled to i~ e the practice of the R-2
reac~on using the N-polyllyd~oAy~l~illes pl~an,d by the above-~iiQr~osed R-l
- reaction ( vith H20 having been ~.IIU~el;i). It is des.l ble to use conc~ ~ion ranges
of the ll l,t~ntc and solvent to plc~v;de a "70% c~nG~ ~ed" (with respect to
- I P ~tAntQ) ~ iO~ W~. This 70% cnn~ dt~ u~lw~ provides eYrP1l~nt
35 results, in that high yields of the desired polyl~ ln~r fatty acid amide prv~luc~ are
secured rapidly. Indeed, jnrl;C~tinn~ sre that the r~ihun is ~lb t~nl;~lly complete
within one hour, or le_s. The cQ~ nc~ of the r~lion u~lu.e at the 70~/0
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c~ aLion level provides ease of h~Antlli~ However, even better results are
secured at the 80% and 90% con~ aLion levels, in that ch,o,,.ulo~aphy data
Ale that even less of the unde~red ~cli~ed by-products are formed at these
higher COI~C~ ~1 ~ alions. At the higher co~c~ aLiOlls the reaction systems are
s so---~ more ~liffic~llt to work with~ and require more effi~ent stirring (due to their
initial th~ ne~), and the like, at least in the early stages of the reaction. Once the
reaction pr~ceeds to any ap~-~ iab'c extent, the viscos.ly of the reaction system
decleases and ease of mixing i,-~ ases.
All pC,.Cf'~ 3f ~, ratios and propo.lions herein are by weight, unless oLllc. ~;se
0 ~pec-r:ed All limits and ~ ';CAI values herein are a~pro~ AIe unless olh~, w;~ stated.
FX~MPLE I
Standard Reaction
A reaction ."-b~lu~e con~i~ti~g of about 214 g C12 fatty acid methyl ester
lS (Procter & Gamble methyl ester CE1295); about 195 g N-methyl-D-~ mine, dry
powder; about 10.8 g 25% sodium l-.l}-ylale, and about 37.7 g propylene glycol as a
solvent is used. The reaction ~ressel co~ a one liter, four neck, round-bottom
flask .~_lo., one 300 mm coiled Co~ - -, one 250 ml round-bottom flask; several
ada~tu-~, one agitator with a v ~' le speed motor; one mantle c~ rcle~l to a Therm-
20 O-Watchg) for le ll~. alulC control; and a ~_cuulll water &s~llalor for va~iuulll.
The methyl ester is added to the reactor and, with ~~ , is heated to about
60~C. The propylene glycol and the N-methyl g31l~Amin~ (puwdc,.~,d), are added with
~lffi~i~P,nt ~ n to keep the solids ~spPn~le~l The twl~c~alu e is raised to about
80~C and a v Illlm of about 100 mmHg abs. is created, if more than about 0.1%
25 ..~;;,~ is present, to e~ A-IG the moi;.lu-e. The p,~ is raised with n.liu~enand the sodium .ll~ lylalc is added. The le,ll~,.alulC, is set at about 80~C and the
time is set at zero. The pre~e is reduced app..,~ ly every thirty ~ s from,
~PP~ 500 to 350 to 200 to 100 mmHg. The pr~ .e is again raised with
l~l ùgwl and a sample is taken for GC analysis.
The above i.landald reaction results in about 20~600 ppm cyclic rnAteriAAI
which is con~ Pred undesirable. In one standard reacfion, the level of cyclic is 250
ppm while the percent col-~e.:i,on is 91%; lc w~ t,he reaction twlllJ~.alul~ to about
70~C lowers the cyclic level to about 80 ppm and the CG~ On to about 88%;
lu~._.h~g the reaction time to about one hour dec.eases the cyclic mAtPri~le to about
3s 50 ppm and the co~ on to about 89%; cutting the catalyst level in half reduces the
cyclic ~tPrj~l~ to about 90 ppm and raises the CGll~w~Ol to about 93%; rw..ovlll~
the .~ nol in 30 ~ les l-,.luces the cyclic m~tPri~le to less than about 50 ppm and
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raises the co,l~e.~on to about 90%; and red~ g the ~uum to a ~ of about
200 mn~Ig reduces the cyclic m~teri~le to about 40 ppm while r~io~ng the
COI.~oll to about 87%.
l~oducing the time to remove the ~ l and redl~;r~g the vacuum have the
s most c~ impact onred~l~ing cyclic formation.
Color ull~Jr~.,.,wnl is obesined by using rÇ~ct~ntc with better color. The
methyl ester and POIY1IYdrOA~r amine should both have a Gartner color of less than
about 1, the amine being the most ~ o~ . Using an excess of amine in the R-l
n, e.g., about 100% excess and/or higher heat ~ 'P-'I te~ e.a~-,s provide
0 illlplu.~.d amine color. Use of a cryst~lli7~tinn step ~ es the color even more.
The amide is p~.fw~bly treated with an ion ~ g4 resin, or, more p~fe.a~ly,
with both anionic and c~ti~n;C ion ~ ~ol.~ resins, to rernove color b~odies. This
l is P~ ~,pli~hF d as follows.
F~A~IplF ~
lS An overall process at the 80% Ic~l2ult co-~c~ aLion level for the amide
sy"~ s~s is as follows.
A reaction ..~lu.e co~ of about 84.87 g C12 f~tty acid methyl ester
~Procter ~ Gamble methyl ester CE1270), about 7~ g N-methyl polyl,yd,o~~ c
per Example L above, about 1.04 g sodium ~--F ~ and a total of about 39.96 g20 methyl alcohol (ca. 20% by wt. of .~clio~ UrC) iS used. The ,~lion vessel
cc....l" ;c~ s a ;,~ld~.l reflux set-up fitted with a drying tube, col-dF-~e ~ and
...Fcl-~nir~l stirring blade. The N-methylglllc~ r/~ nnl h heated with stirring
under l~,l,ùgcn (reflux). After the sol-~tion has lc~cl-ed the desired ~l-yc~alurt~ the
ester and sodium meth~Yi~e catalyst are added. The reaction ~.~lure is .~ d at
25 reflux for about 6 hours. The l~aclion is Ç~5f~ lly t: F'-l in about 1.5 hours.
After removal of the ,-~ ol, the l-,cu._.ed pro-lu.;l weighs about 105.57 grams.CL.)~ography inrlirinte~s the pr~_~ellce of only traces of u"de~d ester-amide by-
prcducts, and no de ~ b~ cl;~edl by-pr~,dL~
While the ru-~u,--g d:Crlo..~,~c generally relates to a solvent-~ciQt~ method
30 for plCp~L N-methyl pOl~ Lor.r amines, such 8S N-methylgl~ -:--r, ss well as
their fatty scid amide d~;~aLi~es using fatty methyl esten, it is to be understood that
~ v~ ti~nc are available which do not depart from the spint snd scope of this
.lLion. Thus, I~ g sugars such as ~uctose, g~1~cto5~ nl~G5~, msltos~ and
tose, as well as sugar sources such as high d~hu~ corn syn~p, high liu~;lûS:e corn
3s syrup and high m~ltose corn syrup, snd the lice, can be used to prepare the
polyl,~dro~,l-ne tn~ten~l (i.e., to replace ~ A~ ) ofthe reJ~
S~ ;ly, a wide variety of f~ts and oils (trigl~ ,.ides) can be used herein in
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place of the fatty esters ~mplified above and can provide an unobvious
ro~ in the degree of compl~t~n~cs For ~ ?I~ fats and oils such as
soyl~l oil, eullo~cp~ed oil, sunflower oil, tallow, lard, safflower oil, corn oil, canola
oil, peanut oil, fish oil, .apcsced oil, and the like, or hardened (I.~droy~ ed) forms
s thereof, can be used as the source of l~i~c~.ide esters for use in the present process.
When the hi~ ly.~ ides are used, the reaction p-~,ceeds to be closer to ce . ' ~inn and
there are less by-products to be le...o.~d. SperifirA-lly~ greater than about 95%
c~ fi~n is possible. F~re led triglycerides are palm kernel oil, coconl~f oil, palm
oil, and ta11ow.
lo Purification
The ~CllrfAC~f~ntc produced by the processes Jic~l~ sed above are ;,.u~.;si..~
pure. However, for ~,.~&lalion of very clear products, even greater purity is
le.luil~.d. The~efole, it has been found l~eC~ to treat he ~rfAAr~f~nt product herein
by at least one of h~ ; sPlo~ed from the group col.~ of reductive b'e~.ehin~ and ion ~ h ~A I I ~
l~e~ucl;~e ble~chi~ is well known as a method of re~ ring/~ g color
bodies and/or color body pre~iul~ that are co~ .led to color bodies later by action
of light, oxygen, hlle~a.,lion with other m~t-ori~l~, etc. However, in order to treat the
N-alkyl polyl~Lu~.~r amine amide ~rf~r,fAnt herein, it is ~ce~ to tske p~CC~ inn~
20 to avoid soap fC,~ AIi~ as fticrl~ scd ~.c.n&ll~
The use of l-~ûg~.l and hydrog, ~,~I;n~ cstslyst csn also provide good
reductive b'-- ' in~ wilhout ~ DD;~_ soap rO....~I;O~- ~lthnu~h this techni~lue usually
is more comrlic~ted and re~lu,r~s special e~ rc..cd hydro~;f n~tion
cstslysts sre those ~e~ . ;t-ed h~.c ~.t-. fv~ c.
2s It will be ~p.ec;ated thst the tn~mlf~lre of dct~ lrf~rt~nt~ from such
l~...._b'el~_au-~eDis 8ni~po~L~Ladva~ ~e of the present process. The present
proCess is p&~ r useful when pl~i~ the longer-chsin (e.g., Clg) and
7III~ ~ed fatty acid PO1YI~ AY amides, since the l~-lah~ly mild reaction
tf...~.~ureD and contl;tinnc herein afford the desired products with ..~ l by-
product form~tisn A pre-formed pofion of the polyl-~dlu,.~ fstty acid smide
Yll f~ -.l csn be used to sssist initi~tinn of the R-2 amide-fo. .--:~g reaction when
L~.,~;des or the longer-chain methyl esters are used as f~ ~.C~
Fx~MPT F m
p"~;~r_l;o~ of N-methyl g11~c~minf pn~ceeds as follows.
3s A~P1'O~ 2500 g of q~ oll~ sol~ltinn cQ~ g about 45% by weight
c~--- ~f!~w~ grade N-methyl ~ ris cl~g~d to a rotary c.~o.~or where it is
heated to about 71~C under about 27.5~ of Hg v m until about 957 g Of
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con~ q~e is c~ cted colr._spo~ldmg to a solids CO~ aLiO-~ in the e~yolalor
residue of about 75%. The residue is mixed with about 660 g of al~h~dlous ...~ Oand cooled rapidly to about 1-2~C using an ice bath ~Le.cupoll N-methyl glllc-Am;r.
cryst~lli7Ps yielding a white slurry. An app~ .rt~l~ 1100 g portion of slury is
s cl~ed to a Waring blender where it is n~ixed for about 3-4 ~ cs before being
filtered using a R~rhner funnel. The sample was filtered to dryness before beingwashed twice with about 165 g ~liq~loP of chilled (about 5~C) .~ OI and once
with about 330 g of chilled ~--~ nl The final cake yields about 438 g of pu~iffed N-
methyl gh~cA~ at about 16% volatiles for a yield of about 83% of the solids in the
io original feed.
The following table illu~ .tcs the color and heat stability .."~,o~e."c,~
g~,n~.aLed by this procedure. The pl-nfiPd crystals are dissolved in ~ t;lle~ water to
yield the same cQ..cr~ aLon of solids as the original feed. Color is ~ d on the
. I~AS as percent hA~ IAnce using a Milton Roy Spe~ ol).c 21D sl,e~,t,u~ t- r inan about 21 cm cell at about 420 nm. The ~ " 'es are also tested for heat stability by
s bje~tin~ the mAteriA1 to about 180~C in an oil bath under an inert ~ os~; ., for
about 1 hour. The treated samples are re-diluted to about 50% con~ alion to
mske up for any water lost during heat l~ n~ and the .ubse~ nt colors are read.
S~qn~le Original Feed Purified C~ystals
Initi~ color 71.9% T 94.8% T
Color after heat ~ 18.8% T 89.0% T
Example IV-A
2s (Amide P'~)&aLiOn with Non-Cry~tAl1;7Pd Amine)
n r~ s~ tion (about 332.62 g) of G~P ~ de N-methyl
~A ~ CC~ n~ about 54% by weight solids is cl~c;l to a ~ d&~d one liter
flaslc set up cc~ ~ a . . ~ A ~ ing blade, cQI~1t ~ ~ and I CC~;~ ~.
Over the course of about one hour and twenty ~ , the soll~tinn is graduslly
heated to about 132~C snd the pl~ss~llc iS reduced to about 66 cm Hg ~r Clll~m to
remove the water which is cc~n~1P;l~ed and co1l~cted in the recei~
To the dried N-methyl gl-~cAmin-P~ is added about 201.71 g of Procter &
Gamble CE-1295 methyl ester and about 37.20 g propylene glycol. After stirring,
about 15.01 g sodium ~ u~:de sol~ltinn (about 25% by wgt. in ~ nl) snd about
3s 14 g .~ nl are added to the reactor and the time is l.,co--led. The mi~cture is
allowed to cool to about 85~C as I~ O1 is ~ lPd offunder al~ s~ ;c plcs~e.
After about 30 ~ q no more ~ ol is visibly A~ ;n,~2 SO vacuum is slowly
applied to the reaction vessel to strip out the ~ n~ ",f I~ OI and drive the
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reaction to comrl~ion When the ~acuunl reaches about 66 mm Hg without
fio~min~ the reaction is comp~ er breaking the V~;UUlll vith n il,ogen,
about 126.86 g water and about 74.60 g ethanol are added to the ~ u,~. The
res ~lting glucose amide so' -tinn is dark yellow in color and ~1~eE~SU1eS about 54.9%
5 Tl,~ ee at about 420 nm.
FY~ , 'e IV-B
(Amide Cryst~ 7~tion with CrysPlli7pd Amine)
A reaction l-~Lule CO~ c~ g of about 121.0 g of purified N-methyl g~ min~
filter cake from FY~mrle m (about 16% volatiles), about 112.1 g of Procter &
0 Gamble C~1295 methyl ester and about 19.7 g propylene glycol are ch& cd to a one
liter r~_Lion vessel e~luil ~,ed with ,-,P~ l stirring blade, cc~len~- and leCei~
The .,~lu-, is heated with stir ing to about 80~C and held under a slight ~s ~lllm for
about 30 }--;-~ cs to remove any residual l~oi~lul~ and .~ --nl from the filter cake.
After brealcing ~ uu", with l~ill'u~Cn~ about 8.4 g of about 25% sodium
lS - Il.n~;~e sol~tinn is chal~.,d to the reactor and the time lecGlded. M~ l isallowed to distill off and is collected in the lCcG,~w. After about one hour, v llm is
slowly applied to strip out the ~ ---,g ~-- ~ ol and drive the reaction to
~,c ~'otion After about two and one half hours ts~rget Va~,UU~ iS ;~ ,d and no
more ~ sllnl is rlictilling Vacuum is broken with nitrogen and about 65.1 g
~ictill~od water and about 39.5 g ethanol are added to the mi~cture. The resultant
glucose amide so1 ~tinn has a very pale yellow tint and ".ez~ed about 88.9%
Tl;...~.~-;ll~--ce at about 420 nm.
FXA~LE V
The rc~en~,.nlioll of strong base anionic ion ~ e resin after exhaustion by
25 polyl.~JruAr amide elution is conflucted as follows.
F.th~nnli~ HCl Sol.~tion iS p~ d by adding about 27.4 g of cQ~F-.~-nlct
(about 36.5 wgt%) HCl to about 972.6 g 3A eth~r~nl
A tilute caustic s~ tinn is plepalct by dissolving about 15.3 g of NaOH
pellets (assay = about 98%) into about 1484.7 g of .li~illed water.
About four l,un~ct-fifty ml. of c-1- ~-,~ A.. b. .l:le IRA-410 resin is packed
in a 500 ml ~ntlualed d'~F-'~ cylinder and is washed with about one liter warm
~lictill~d water to remove residual amide. The resin is washed with about one liter of
about 5% Fth~noli~ HCl so1 ltinn (prc~)arcd as dP~ ed above) to acidify, followed
by washing with about one liter of ethanol to ~s , '~ ~ the removal offiltty acid. The
3~ resin is then washed with about one liter of warm ~ictillF~d water to l~hydlnte the
res n.
The resin is then l~enF-atcd by slowly eluting about 11/2 liters of about 5%
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~ql-eous NaOH sol~ltion through the resin. T}se res?n is then washed wsth ~ictilled
water until the pH is about 8.
The ~en~.~lion of strong wid e~tionic ion ~ resin after ~ inn
by polyl-~Lo~ amsde elution proceeds as follows:
F.th~nn~;~; HCl sol .I;nn is p~s~d by adding about 27.4 g of c~
(about 36.5 wgt%) HCl to about 972.6 g 3A ~th~nnl
About four l~ul-~r~ d-fifty ml. of ~ e~ 120 Plus strong acid
c~tinnic resin is packed in a 500 ml g,ndu~ed d;e~e~-c;-~g cylirsder, ~ d irs about a
50~C heating tape and is washed with about one siter warm .lictill~od water to remove
0 t,-,e s~s?~hl~l amide product. The resir~ is a~ ed by elut?ng about one "ter of
eth~nnlie HCl and is then washed with warm dictill~od water to l~hydl~e the resin.
Regcne.~l;on is c ~ d by slowly eluting an ~dd;ti-~n~l liter of about 5%
~queous HCl lhluugll the resin. The resin is then washed with ~icti1led water until
the pH is a~pr~;...A~Cl~ 5.
lS FX ~PLE ~1
About two l.~lJ~ t mls of l~5CIl~ .alcd ~ c~ 120 Plus from Example
VII is packed in about a 250 ml ~~ cd c~l;,ldcl wl~ped with a heating tspe set at
about 50~C. About two l~ 1 grams of glucose amide which is pl~,d from
cryctA1li7ed N-methyl g~l~c-Amine in P~ ~ ~ dallcc with Example IV-B is eluted II~IUU~
20 the resin and is coll~cted in about 200 g ~ otQ
About 1800 g of eluate from the c~tinn;C column is then eluted lhluugll about
200 mls of r~e.~ G IR~10 strong anionic resin from Example VII.
This column's ~e~ .alun, is also I~ d at about 50~C with the aid of an electric
heat tspe. The eluate is cQllPcted in sixteen, about 100 g A-liq~lote
2s Before resin l-~ , analysis of the glucose amide in~ir~t~e the following
al~pl~ quality and cQ~.pos ~inn
Tln~ rc at about 360 nm = 74.1%
N-methyl g~ Amin~ = 2.8%
Fatty A~id/Methyl Ester = 4 9%
30 C;l~lcose amide = 55.6%
Ester Amide ~ 0.2%
~ After resin LICA~ , both the color quality and r~n~pos;tinn of the product
are greatly Ullpl~
3s Tln~ A~ce at 360 nm = 93.3%
N-methyl ~ J "';"f 5 0.1%
Fatty Acid/Methyl Ester = 0.6%
~ cose amide = 55.5%
Ester Amide = 0.1%
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FXAMpLE VII
A second method for r~cll~.alion of strong base anionic ion ~ e resin
after ~ by polyl~ydluAy amide elution is conAIlcted as follows.
FthAAn-lic HCl sQ1~ltion is ple~ d by adding about 27.4 of cQI~c~ lcd
s (about 36.5 wgt ~/O) HCl to about 972.6 g 3A eth~An~l
A dilute sol~ltion of about 7 mole ethoxylated lauryl alcohol is p.~p~ed by
dissolving about 9 g of ell,o,-~lale in about 9 g of ethanol and about 1482 g of warm,
Aictil1ed water.
About four hund,cd-f~y ml of ~-l-n~,ted resin, is packed in a 500 ml
0 grad~lated d;~r~ g cylinder, w~?ped in a heating tape and held at about 50~C.The resin is washed with about one liter of warm AiCtill~.d water to remove the
residual amide. About one liter of warm, about 5% aqueous HCl is eluted through
the resin to acidify. The column is allowed to set for about two hours at about 50~C
to allow the fatty acid to migrate to the surface of the resin. The column is back
wa~hed with about 11/2 liters of warm ethoxylate SQl~tion to remove the fatty acid
from the col~lmn
The resin is then .~,g~ lcd by slowing eluting about 11/2 liters of about 5%
aq.,~us NaOH sollltion through the resin. The resin is then washed with distilled
water until the pH is about 8.
The c~Ati~nic resin is l~e.~.,-alcd in the same manner as desc,il,ed in Example
VII.
When glucose amide pl~cd in the manner A~-il.ed in F~~~~ e IV-A,
having an amber color and ~ g about 32.1% T~ Ce at about 360 nm, is
passed ILUugl~ these ion ~ ge resins, the color hl~JlU~_5 to a pale straw color
25 .~.rA~ about 82.2% T.a--~ ce at about 360 nm.
EXAMPLE VIII
N-methyl glllcAminP, with good color stability and which ~-l,s~q~-Pntly
produces good qu. lity glucose amide is ple~d in the following manner.
APP14~ r a two gallon autoclave is chu~cd with about 360g of Grace
30 4200 Raney nickel catalysts as a 50% ;,.~ Q-OI~ in water, about 920g of 50% methyl
amine and about 1000g water. The reactor is pr~ e;i to about 1500 psig with
1,~ Log~. The reactor co~ are heated to about 50~C while stir~ing. To this is
cl~ecl about 2600g of ClearSweat~ 99DE corn syrup and the co-~ arc reacted
at about 50~C for about two hours. Fresh hydrogen is added to II~ I the p,~ ,e
3s as it is C~ '''F~ by the reaction. A sample is rl ."u~. d from the reactor at the end of
about two hours and its co,~.PGS ~ n~e~td to be appr~ - ;--IAIe1~.
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N-methy~ rAmin~ = 95 o%
n-~uco~yl~ne = 1.0%
glucose = 1.0%
sorbitol = o 9%
. s
This mAtçriA-1 was Ught yellow in color and upon s~bse~ ent reaction to
glucose amide in accoldance with the procedure desrribed in FYAmple IV-A results in
a product that is very dark in color.
The reaction ~Lule lc~ in the autoclave is now ~.lI,;e~,le~ to a
0t~llpc-alule ill.;l~,ase from about 50~C to about 100~C over the course of about 60
r..;~ while hydrogen p~,s,~e was "-A~ ed at about 1500 psig. After about
100~C is reached, the reactor is quicldy cooled under LydloO_.I pr~,~ulc by
intro~uring cooling water to the reactor coil. When the ~-~lurt has cooled to about
30-50~C, the mAt~ is L~cl.alged from the reactor. Its co...l os ~;r~ is
lS ap~lu~ y.
N-methyl g1llrA-min~ = 97 3%
n-gluco~l~ c non-clEtectn~'e
glucose non-~:e - ~'F
sorbitol = 0.8%
This water white mAt~riAI is used to produce glucose amide in acco-dsl~cc
with the p.oce.lu-l_ used in FYAmple IV-A and results in a product that is pale yellow
in color.
FXAMPL}~ lX
AMlDES MADE ~OM CRYST~T ~ ~7Fn NMG AND BASE TREAl~ ESI~R
About 49.1 kg of Procter & Gamble C~1295 methyl ester is cl~S~ to a 72
liter t1;Atil1Atinn flask e~luipped with a con~ r and .~ c~._. . About 900 g of sodium
1--J~ scl~ tir~n (about 25% by weight in .-- ~ 'O1) iS added to the ester. At an30 absolute p~l'G' of about less than 10 mm of Hg., the ester is heated to about140~C. The ~ tillAte iS CQn'~ and coll~cted in the ~ r. The first about 618
g coll~ted in the ,.,cei~,r is discarded; the le-n~ g tlicti1lAte is coll~cted as a 'water
white', low odor methyl laurate.
About 175.0 g of n-methyl gl~ e cry~tals purified in &conl~ce with
3s Example m are dissolved in water to produce about 375.0 g of n~eol~c sohl~ionThis sDl-~ti~n is d~ed to a ~lal~d&ld one liter reaction flask set up co~.~r.;~ a
A1 stirnng blade, co~d~n~r" and recG;~,r. Over the course of about two
hours and forty ,~ , the sol~ltion is gradually heated to about 130~C and the
pl~e is reduced to about 26 inches of Hg v~uw~ to remove the water which is
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condenced and coll~cted in the .ecei~.er.
To the de~rL~Lcd n-methyl gll~rAm;ne is added about 195.9 g of the ~ d
methyl laurate d~s_ ;l,cd above and about 36.5 g of propylene glycol. A~er stir~ing,
about 14.5 g of sodium ~ >~i~le sol~ltion (about 25% by weight in ...- 1~ 1) is
s added to the reactor and the time is recorded. The ~l~lu-~ is allowed to cool to
about 85~C as ~--~ ol is tlictilled o~under Alo~nsph~ ;c p~ . After about 30
",~ no more ,~ OI is visibly ~ tillir~g SO ~ m iS slowly applied to the
reaction vessel to strip out the ~ O1 and drive the reaction to
r,c ~p~tion When the v reaches about 25 inches of Hg wilhou~ es;.;~,
0 r~ the reaction is complete. Afier breaking the ~ ,UUlll with l~illug~, about123.0 g water and about 72.3 g ethanol are added to the r,~lur~. The resllltir~gglucose amide sol~ltion is ~ater white' in color and ~ ,S as 95% T1A--~ 11 at
420nm.
FXAMPT F X
AMIDES PREPARED USING TRIGLYCERIDES
Tl;gl~,.;de reAA~tAntC include CRISCO~ oil, palm oiL sun~lower oiL canola oil,
F~l oil, coccmlt oil palm ~teA~;~ e, and the co..~pondi.,~ hy~'~ l oils. The
catalysts are aLkali metal salts of monohydric Alcl~hr~ls or polyh~d,~.A~ coho~ e.g.,
sodium ...~ c~ The r~;liol1 l..F.J;~ iS a .~ o.. c ---- ri c~ e.g., NEODOL~
10-8 or 23-3, or GENAPOL 26-L-5.
The .~_lion is con~ucted in a melt. The N-methylg~ Amine at a mole ratio of
from about 2.3:1 to about 2.9:1 based upon the trigl~.;dc, nol~ on ~ fRrtAAnt and
triglycende are co-melted at about 120-140~C under vacuum in about 30 mimltes.
About 7.5 mole%, based upon the N-methyl Bh~ e of sodium m~hnYirle is
25 added to the reaction lluAIu~. The l~&_lion mixture beG~ rs h.~9~~ ~r~_ in
s~ c The reaction ~IU~ lur~. is ;--...-P-~ e1Y cooled to about 85~C. The reaction
ule is ...~ -rd under V.._uul~l for about 1-2 hours .,nd is w , '~t~ at this point.
In an A1t~rnAte process, the N-~ lgl~,c~ e is muced at room t~"~ lu,~;
with the l~ nic ~-- rr~ L~.,e ;de, and catalyst. The mixture is heated to 85-
30 90~C under, A~ el~, vacuum and nitrogen. The reaction ~lU~Lul~s become clearin one to one and a half hours. The reaction n~lul~ are ~ F~ at about 85~C
for about 2-3 hours.
More spe~Aifi~AAAlly~ about 127.45 g of N-methylgluc~ e l~owder is added to a
500 ml three-necked, round-bottcm flask e~luipped with an internal ~ t~r,
3s ~ m line, nitrogen line, and "~erl-A~ AI stirrer. The N-methylgl-,~A---:-~e is melted
at about 130-140~C and dried under vacuum. Hardened palm kernel oil (about
156.41 g) is added to a s~_~.le 500 ml three-necked, round-bottom flask e.luil~ed
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with an internal ~ ...n~ AtPr and a vacuum line. The hardened palm kernel oil ismelted at about 130-140~C and dried under ~a. uuln. The dried ha..lened palm kernel
oil and about 31.54 g propylene glycol are added to the N-methylgluAAmine with
n~ixing. About 1.76 g sodium mPtho~n~le as a 25% I-~lu~e with ~ AI~nl is added to
s this l~ UI'~, with mixing and the ".P~ is ,~ .w~d by vacuum. The ..~lu ~ is
h~ Gg~ Irol~c in about 1.5 ~ IG~ at which time, cooling is applied. The "~lu~ is
cooled to about 90~C in about seven ...;-~ g and .-.A;--I~;~-rd at this t~.-pe~ ul~ for
about 85 ,..:....l~c The ll~lul~ is pouret out and the analysis was done by gas
c~ '10~ap}'~r.
R~.-lu~lk5 the water from the ~~ aelh ~ s the r~ ;nll of fatty acid.
~rtr~.~bly, the water level is less than about 0.1%.
FXAMPLE X~
TREAI~ OF AMIDE WITH BOROHYDRIDE
About two hundred grams of a glucose smide are sdded to a one liter, three-
lS rlP~ P~1, resction flask fitted with a ~ n~ Pr on a top load bAl~nce. The reactor is
~,~d to a heated mantle and cc~ P iled to a ...P-I.Ani~AI sti rer.
The t~llpc.~luie is raised to, and ~ at, about 38~C lL,c,-~ ou( the
period. About 1.23 g of co~ ,;al sodium bo,ohyd,ide and about 0.20 g
of pu~d~;~l sodium borohydride are added to the reactor.
There is about 0.49 g of sodium hydroxide in the borol~Lide, which raises the
pH from about 8.7 to about 10.4. The starting color of the amide is albout S4%
llu~ cs ~n at 420 nAn-~.... tr;~ and after about two hours of I~A~ r.,l the
transmission is about 76%. The fi,lal pH of the sollltinn is lo~ d to about 8 with
31% I,~Loel-'n- ;c acid.
The pH of 10.4 results in Lc,eas~d pro~luAtinn of soap, but a pH of more than
about 10 is r~u~d for bor~J,;dc ~l~ililr. U"hcsled N~ ll-yl~ c~m;ne amide
typically has a soap content of about 3.09. l~e pH~soap content of borohydride
trcated N-methylgll~r-Amin~ amide varies appro~ Iy as follows: 10.1/3.14;
10.3/3.16; 10.6/3.17; and 11.0/3.41. As a result, the pH should be less than about
30 10.9 turing lr~l-- ~~1
Fx~MpLE XII
Polyll~ld,u~y fatty acid amide S~rfAr~tS~nt SOI,I1tinn as in F ~ 'S II before
~JU~ , having a % 1,~ nA--Iics ~ below about 70~/4 is treated with L ~ ug~n in ahigh pl~_ stirred reactor, heated by an internal coil co~ d to a steam/water
mu~ng apl~&,~lus. The ~ iI so o co c, &l)p~-~ ~ 60% s ~rfA"tAnt
22% water, 12% c~hAnr,I and 6% propylene glycol. About 1000 g of the soI~ltinn is
slu~ied with about 1.2 g of p~IIadi~lm catalyst (5% p~ lm on car'oon) wetted to
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about 50% moisture. The reactor is sealed and the agitator started at about 500 rpm.
The reactor is ~~pealedly (five times) slowly pl~ cl to about 200 psi and then
slowly vented. The reactor is then p,~ ed to about 400 psi and the agitator
increased to about 1200 rpm. The te.~ lu,~, is raised to about 66~C and the
s reaction carned out for about two hours and the product filtered under hydrogen
p-~su-e to remove catalyst. The % Il~ ''Q~is now more than about 80%.
