Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ ~ ~5~ 7
The present invention relates to a process for the
manufacture of carbamates by reaction of alcohols with urea in
the presence of ion exchangers containing nickel.
Houben-Weyl, Methoden der Organischen Chemie, volume
8, page 190 et seq. discloses tha~ alcohols may be reacted
with urea to give carbamates. The yields from the process are
unsatisfactory, even using a fairly long reaction time and a
large excess of alcohol, since by-products, e.g., biuret,
allophanic acid esters and cyanuric acid, are produced~ It is
true that the yields can be improved by using zinc acetate,
lead acetate or cobalt chloride tZ Naturforsch., 1 (1946), 520)
or using metal salts and metals, of which æinc dust, zinc oxide,
vanadium pentoxide, tin~IV) chloride and tin(II) chloride, ;;
zinc salts, manganese acetate, chromium acetate, lead acetate,
uranyl acetate,_~ilver nitrate and copper sulfate have been
given as examples (German Patent 752,127). However, the
carbamates thus obtained still contain a certain proportion of ~;
the above by-products, which precludes their use in all syntheses ~
.,. . -
which require starting materials of the highest purity. ~hus,
eg. such crude carbamates cannot be used directly for the
manufacture of dimethylol compounds which are employed as
finishing agents for chlorine-resistant finishing of textiles,
and inst~ad must first be -purified by renewed distillation, or
recrystallization.
If the method of the above, German patent - which
does not mentio`n nickel salts - is followed, and the metal
catalysts described are used, with glycol monoethers in place
of monohydric alkanols as the starting materials, it is
not onIy the purity of the end product but
~ -
-- 1 ~ :
.
~ 5 ~ 1 7 o,z. 31,037
f also, in many cases, i~s yield which is unsatis~actor~. The Table
whlch ~ollows shows the results obtalned in reactln~ urea with me-
thylglycol (molar ratlo 1:~) to give methoxyethylene-carbamate.
TABLE
(Reaction temperature 130C, reactlon time 25 hours)
Catalyst Amount of catalyst Yield based on
based on urea (~ urea (% o~
by welght) theory) ; ;`
,................................... ~ : ~: .i
Boron tri~luorlde 1 50
Aluminum acetate 5 55
Manganese sulfate 5 57
Sodium aluminate 5 58 ~;~
Sodium tetra~luoborate 1 63
Copper ~ilings 70
Tin(IV) chloride 5 ~5
Further, German Published Application 1,64~,635 disoloseqZ the ~ -
manufacture of hydroxyeth~lene-carbamate ethers by reaction Of
ethylene glycol monoethers with urea at ~rom 100 to 150C in the
preSeDCe 0~ ni~ckel compounds. It is true that the yields are 94% o~
theory9 but, as shown by the Examples, reaction times o~ at least
.~ . .
10 21 hours are needed. Nickel compou:ds, in the said application, ~ ~`
mçans nickçl salts3 nickel chloride is employed in the Examples.
Ik is an ob~ect of the present invenkion to provide a nqw pro-
, . .
cess by means o~ which a large number o~ carbamakes oan be manu-
I ~actured more simply and more economically, in better yield- and
Z~ pur~ty and with a better space-time yield.
" .
1 We have found that this ob~eck is achieved and carbamates of
.~1
the ~ormula
¦~ R ~ o-R2 ~ 0 - C - NH2 I
where Rl is an aliphatic, cycloaIiphatic or araliphatic radical which ~1
0 0 H `
may be interrupted by one or more C o or C N groups and/or
oxy~en atomsJ R is an aliphatic radical o~ at least 2 carbon atoms
-2-
``` 1~5~L01~ ~ -Z' 3R~37 :~
which is optionally interrupted by one or more -C-O~ or -C-N- grouPs
H
and/or oxygen atoms, or is - '3 - ~ where the R3's may be identi-
R n
cal or different and eaoh i5 a cycloaliphati¢, araliphatic or aro-
matic radical, and n is an integer from 2 to 6, and m is 0 or a po-
O
sitive integer, or Rl is H N C ~ or phenyl or ~ if m is not less
than 1 - hydrogen, are obtained advanta~eously by a process wherein
alcohols of the formula
~ ( Q-R2- ~ OH II
where R1, R2 and m have the above meanings, are reacted with urea
- in the presence of ion exchangers containing nickel,
When using methylglycol, the reaction can be represented by
~he following equation~
C ~ OCH2CH20H + H2NCONH2 ~ CH~OCH2CH2OCONH2 ~ NH~.
' Compared to the conventional process, the process of the inven-
'~ tion gives a large number of carbamates more simply and more econo-
mically, in better yield and purity and with better space-time yield.
Compared to the process disclosed in German Published Application
., .
1,64~,635, the new process offers advantaæes ln that the reactio~
time is substantially reduced and ls in general from 5 to 10 hours
and the spaoe-time yield is increased by a ~aotor of ~ , In the
light of the cited publications, it is surprising that the process of
the invention gives a large number of carbamates by a simple method,
in better yield and purity and wikhout formation of by-products. ~he
carbamates obtained by the ne~ process con~orm to the highe$t stan-
dards of purity and can, eg.~ be reacted, without prior puriflcation~
w1th ~ormaldehyde to give the above dimethylol compounds used for
chlorine-resistant textile finishes, thereby offering a labor-savin~
and more economical method of manufacture of assistantsJ eg. ordinary
textile finishes and resin textile finishes. Particularly in view of
-3- `
l~S~ o, Z. ~1, 037
German Published Application 1,643,635, it would have been expected
that the new process would not give better yields and better purity
and would even glve poor~r results, since - contrary to the teach-
ing Or the said published application, according to which only nickel
salts should be used7 in amounts Or rrOm 0.1 to 5% by weight based
on urea - the process Or the invention ls carried ou~ with cation
exchangers and the nlckel bonded as a cation to khe exchanger. A~-
ter completion o~ the reactlon, neither nickel nor dissolv~d nicke~
salts remain ln the reaction mlxture and such salts can thus, in the
light of the process described in German Published Application
1,643,635, not react with the carbamate formed so as ~o i~duce a
reverse reaction or the rormation o~ undesirable by-products. The
process according to the inventlon o~fers a furkher advantage that
the ion exchangers containlng nickel can be re-used as frequently
as desired without regeneration.
The starting materials used are urea and alcohols Or the ror-
mula IIo Pre~arred starting materials II and, accordingly, pre~erred
l end products I, are those where Rl is alkgl of 1 to 18, pre~erably
!~ 0~ 1 to 10? and especially of 1 to 7~ carbon atoms which may be in- ~:
2Q terrupted by several, or ln parti¢ular by o~e, -C o or C N group
and/or by oxygen atoms, pr~ferably by from 1 to 6 and especially 1
or 2 oxygen atoms, or R is og¢loalkyl o~ 5 or 6 carbon atoms or
aralkyl of 7 to 12 carbon atoms, R is alkylene Or 2 to 18, pr~er-
ably 2 to 10, and especlally 2 to 7, carbon atoms Which may be inter-
O 0 H
rupted by several, or in parti¢ular by one, -C o or C N group
and/or by o~ygen atoms, preferably by from 1 to 6 and especially
1 or 2 oxy~en ato~s or R2 is alkylene of 4 to 18~ pre~erably 4 to
10, ~nd espe¢ially 4 to 7, carbon atoms whioh may be interrupted
0 0 H
:~ by several, or in partioular by one9 C ~ or C N ~roup and/or b~
~O oxygen atoms, preferably from 1 to 6 and especially 1 or 2 oxygen
atoms, and is advantageously the radical~ ~ 1 where the R4~s may
LR4~ ~,
be identlcal or different and ea¢h is hydrogen or ~lkyl o~ 1 to 7
-4- ; `
.
l~)S~0~ o. z . 31, 0~7
carbon atoms and n is an integer from 2 to 6, pre~erably 2~ ~ or 4,
or H where the R3's may be identical or dlrferent and each is
- C - _ ~:
_ R~ n
cycloalkyl of 5 or 6 carbon atoms or aralkyl o~ 7 to 12 carbon atoms
or phenyl, and n is an integer ~rom 2 to 6, preferably 2J ~ or 4,
and m is O or an integer ~rom 1 to 50, preferablg from 1 to 28~ and
: , o
especially 0, 1, 2, 3J 9 or 18, or Rl ls H N-C J phenyl or - if m
is not less than l - hydrogen. I~ m is greater than 1~ several R2's,
which may be iden~ical or di~ferent~ are present. The above radicals
may ~urther be substituted by groups which are inert under the re~
action conditions~ e~. alkyl or alkoxy each of 1 to 4 carbon atoms,
carbamoyl, carbalkoxy of 2 to 6 carbon atoms~ hydroxyl or ¢arbamato.
;l The urea may be employed in the reaation in a stoichiometric
amount or less, pre~erably in an amount of ~rom 0.5 to 1 mole per
mole of starting material II in the case o~ a ~r~e hydroxyl group.
.1 .
If 2 hydroxyl groups are present, the monocarbamate is suitably ob-
tained i~ ~rom 0.5 to 1 mole o~ urea is used per mole o~ starting
material II, mixtures of monocarbamate and dlcarbamate are obtained
;~ larger amounts o~ urea, o~ up to 2 moles per mole of starting
material II~ are employed, and ~he dicarbamake alone is obtained i~
20 ~rom 2 ~o 2.5, pre~erably rrOm 2 to 2.2~ moles o~ urea are employed
, per mole o~ starti~ig material IIo Analogously, in the case o~ pol~-
hydroxy-aloohols, it is possible, by using stoichiometric or cor-
respondingly reduoed amounts of urea, to produce monocarbamatesJ di-
carbamates, tricarbamatesJ tetracarbamates and polycarbamates in the
pure ~orm or as a mixture o~ carbamates~ whereo~ the components de-
pend on the molar ratio of the starting materials and the number of
,; hydroxyl groups in the alcohol II~ Thus, eg., depending on the mo~
I lar ratio Or ureaf the alcohols shown below can gi~e the following
~ corresponding carbamates:
--5--
:
~05~7 ~:
~, . .
Alcohol Carbamate
OCH2CH2CH20H HC~2CH2CH2CNH2 and
H2NCoOcH2cH2cH20cONH2 '.~ .', ~'
: HOCH2CH2CH2CH20CONH2 and
HCH2CH2CH2CH2H
H2NCOOCH2CH2CH2CH20coNH
HOCH CH = CH-CH OCONH and
HOCH2CH = CH-CH20H 2 2 2 -~
H2NCOOCH2CH = CHCH20CONH2
HOCH CH OGH CH OCONH and
HOCH2CH20CH2CH20H 2 2 2 2
H2NCOOCH2CH~OCH2CH20CONH2 ~ -:
,
: CH CH CH CH
3 1 3 1 3 ~ 3
. HOCH2-C-COOCH2-C-CH20H HOCH2-C-COOCH2-C-CH OCONH2,
. CH3 CH3 CH3 CH3
_~ CH3 1H3
H NCOOCH -C-COOCH -C-CH OH and
I ' ~'
CH3 H3
, :~ . CH3 f 3
~ ; H NCOOCH2-C-COOCH2-C-CH20CONH2
: ~ 2
CH3 CH3 :`
- ---- ...... .
: Preferred starting materials II are: C4HgOH~
ClOH210Hl C17H35~I~ C6H130H~-OH, ~-CH20H, CH30cH2cH20
' C2H5CH2CH2H' C~I30CH2-CH-H' C2H50CH2-CH-H' C4H9CH2CH2H '
; ~ -CH2cH2H~ ~ -OCH2CH20H, HOCH2CH2CH20H, HOCH2CH2CH2CH20H,
HOCH2CH=OEI-CH20H, HOCH2CH2CH2CH20H, C4HgOCH2CH2CH2CH20H~
CH3 ~H3
4H9CH2CH2CH2CH2~H2C 20H and : H C IC
CH3 CH
However, it is also possible to use, eg., the following
alcohols as starting materials II~ l,3,5-trihydroxypentane,
2-acetoxy~
-- 6 --
ethanol, 2-acetamido-1-ethanol, cyclopentyl alcohol, phenylethyl
alcohol, decyl alcohol, octadecyl alcohol and the following
alcohols, which are either unsubstituted or substituted, at
the w -hydroxyl group, by the radicals specified or the radicals
described in connec~ion with the above preferred individual
alcohols II. hydroxypropyl-(l) alcohol, hydroxypropyl-(2~
alcohol, hydroxy-n-butyl~ alcohol, hydroxy-n-buten-(2,3)-
yl-(l) alcohol, hydroxyethoxyethyl~ alcohol, triethylene
glycol, hydroxy-pivalato-(3)-neopentyl-(1) alcohol, a-hydro-
xyacetylamido-(3)-neopentyl-(1) alcohol,~-hydroxydecyl~
alcohol,~-hydroxy-2,4,6-triethyl~octanyl-(1) alcohol, 2-
hydroxy-2-cyclohexylethy1-(1) alcohol, 2-hydroxy-2 benzylethyl-
(1) alcohol, 2-hydroxy-2-phenyl-ethyl-(1) alcohol and 6-
hydroxyhexyl-(l) alcohol.
The ~action is as a rule carried out at from 100
to 160C, preferably at from 125 to 150C, under atmospheric
or superatmospheric pressure, continuously or batchwise~ In
general, the starting material II also serves as the reaction
; medium though, if appropriate, organic solvents which are
inert under the reaction conditions may be used, eg. aromatic
hydrocarbons such as benzene, toluene, ethylbenzene, o-, m-
and p-xylene, isopropylbenzene and corresponding mixtures.
The amount of solvent used is suitably from 200 to 10,000%
by weight, pre~erably from 200 to 1,000% by weight, based on
~tarting material II. If the alcohol II alone is the reaction
. .
medium, an appropriate additional amount thereof is added to ;
the starting mixture. ;
The reaction is carried out in the presence of ion -~
exchangers - as a rule acid ion exchangers, and pre~erably
acid synth~tic ion exchange resins - which contain nickel.
Such exchangers include all the cation exchangers described
in Houben-Weyl, Methoden der Organischen Chemie, volume I/l,
~ - 7 -
". ~ , .. . .. .
1051~7
page 528, Table 3. Exchangers of strong to medium acidity,
eg. phenolic resins or polystyrenesulfonic acid resins, or
exchangers containing appropriate acid resins, eg. bifunc-
tional condensation resins, are used preferentially. It is
also possible to use polystyrenephosphonic acid resins, poly-
. .
,; ' .
'
''
.:
. , .
j ~
,, .
,
:~ :
;: :
~ .
.
:
,~: .
~; '
':: :
L7 oOZ. ~1,037 ~
styrenephosphinic acid reslns~ resorcinol resins and aliphatic or
aromatic carboxylic acid resins. The above cation exchangers are
commercially available, eg~ under the re~istered tradenames Amber-
lite, Lewa~lte, Lewasorb and AmberlystJ specl~ic examples being
Amberlyst 15, Amberlite 200, Lewatit CA 9259, Lewatit S 100 and
Lewasorb V 100. Before the reaction, the exchangers are charged
with nickel in accordance with oonventlonal methods, suitably by
a treatment with solutions, advantageously aqueous solutions, o~
nickel salts. Sul~able nickal salts are nickel chloride, nlckel
; 10 aoetate, nickel bromide, nickel nitrate andJ prererably, nickel
sulfate. The nlckel compounds may also be in the form of corres-
ponding h~drates, eg. nickel chloride hexahydrateO However, nickel
phosphate, nickel carbonate, nickel bicarbonate, nickel borate,
nlckel oxalate and nickel propionate may also be used, Before treat-
ing the exchanger, the water which may be present in the exchanger
can be removed by passing organic solventsJ such as alcohols, eg.
methanol, ethers, eg. glycol monoethers or tetrahydroruran, or
acetals, eg. of ~ormaldehyde, through the exchanger. Preferably,
the exchanger is activated, prior to the treatment with the nickel
salt, by means of an acidg suitably sulfuric acld, hydrochloric
acid ar the acid corresponding to the anion of the nickel salt. The
exchanger is advantageously first left ~or ~rom 10 to 30 minutes
under or in water at from 15 to 40C and is then activated for from
10 to 60 minutes with acid, suitable in the form of an aqueous
solution o~ from 2 to 15 per cent strength by weight, at from 15
; to 40C~ after which the exchanger is washed with water until
neutral.
The treatment with the nickel salt solution is suitably car-
rlçd out at from 10 to 50C, pre~erably ~rom 20 to 30C~ It may be
~0 carried out under atmospheric or superatmospheric pressure~ batch-
wise, egO by a stirring-in or batch method, or, preferably, con~
tinuously, eg~ in exchange columns, in a fixed bed, flowing bed or
fluidized bed in tr~ycolumnsJ Suitably~ nickel salt solutions of
~ ~5 ~ 7 o~zO 31,037
rrom 5 to 50 per cent strength by weight are used, the treatment
times belng from lO to 60 minutes. A~ter the treatment, it is ad-
vantageous to rinse the exchanger with water until the wash liquor~
or the wash llquor issuing from the exchange column, gives a neutral
reactionJ and then to wash the exchanger ror from 10 to 60 minutesS ;`~
at from 15 to 40C, with one Or the above inert solvents or an al-
cohol~ in the case o~ liquid alcohols II preferably with the parti-
cular alcohol II which is to be used (ror the reaction), until the 1~ ~;
exchanger is substantially free from water. Suitably, one part by
weight Or exchanger is charged with rrom 0.01 to 0~2, prererably
from 0~02 to Ool~ and especially rrom 0002 to o~o8, part by weight
o~ nickel, and rrOm OoOl to 0.259 prererably rrom 0002 to O. 1J part
by weight of exchanger is then used per part by weight Or urea.
The reaction may be carried out as follows: a mixture of urea,
starting material II, exchanger and, where used, the solvent, is
kept ror from 7 to 12 hours at the reaction temperature. It is ad- ~
vantageous to remove the ammonia produced during the reaction ~rom ?. I ,
the reaction solution by passing nitrogen through the latter. The
l reaction mixture is then cooled and riltered. The end product is iso- ;
j 20 lated rrom the filtrate by conventional mekhods, egO b~ distllla-
tion. The unconverted starting material II and the ion exchanger
¦ containing nickel, which has been filtered o~, can be returned to
the reaction.
The compounds which may be manufactured by the process Or the
invention are valuable starting materials ror the manufacture Or tex-
tlle finishing agents, dyes and plant protection agents. For ex- ~ -
I ample, they oan be methylolated to glve textile finishing agents
¦ which give a good wrinkle-resist e~fect and ~inlshing effect to-
¦ 3 gether wlth a so~ter, harder or ruller hand~ dèpending on the
structure of the rinishing agent. Information on uses may be found
in the publications clted earlier
In the Examples which follow, parts are by weightO
,' ''
_g_
.
~ 0 ~'~ o,z ~1,037
EXAMPLE 1
a) Manu~a ~
A column is filled with 1,000 parts o~ cation exchanger/ which
is allowed to stand in 1 J 000 parts of water ~or 15 minutes. 500
parts of 10 per cent strength by weight hydrochloric acid are then
added, the column is le~t to stand for 20 ~inutes and the catlon
exchanger is then washed neutral with distilled water. 3~400 parts
Q~ a 10 per cent strength by weight solution of NiS04.7H20 are then
charged onto the activated exchangerO When the solution leavlng the
column no longer reacts acidJ the uptake o~ nickel salt has ended.
The exchanger charge is washed neutral with water and then washed
free from water with dioxane or the fluid alcohol II to be used ~or
the carbamate synthesis. The exchanger is now ready to use and con~
tains 0.065 part of nickel per part o~ exchanger.
b) Reaction
~CH2CH2CNH2
A mi~ture o~ 300 parts of urea, 684 parts o~ methylglycol and
18 parts of a cation exchanger which is commercially available un-
der the registered name Amberlite 200 and, having been treated in
acoordance with Example la), contains nickelg is heated, with stirr-
ing, to the reflux temperature (130C) in the course of 20 mimltesJ
in a stirred apparatus equipped with a reflux condenser. After
reaching the reflux temperature, a slight stream of nitrogen bubbles
is passed through the reaction mixture. The reflux temperature rises
to from 148 to 150C in the course Or 5.5 hours, The reaction tem-
perature is then kept at 149C. After a tokal reaction time of 7
hours, the reaction solution is cooled to about 120C and the ex-
~ changer is filtered off.
.1
Excess methylglycol is distllled off under reduce~ pressure.586 parts of methoxyethyl oarbamate are obtained. This corresponds
to a yield of 98.5% of theor~ based on urea employed. On distilling
~ the carbamate at a pressure of 0.1 mm Hg, a dlstillation residue of
i only o.8~ by weight is le~t. The carbamate has a boiling range of
--10-- '
-
~ ~5 10 ~7 o.~. 310037
from 96 to 98C at 0.1 mm Hfgff
EXAMPLE 2
CH~OCH ~ ~ ~
CH-OCONH2 : :
300 parts of urea, 810 parts of methoxyisopropanol and 18 parts
of a cation exchanger which is commercially available under the ~ ;
registered name Amberlite 200 and, having been treated in accord~
ance with Example la), contains nickel, are mixed in a stirred ap~
paratus and the mixture ls heated to the reflux temperature (125C) `~
in the course of ~0 minutesJ whilst stirring~ The mixture is then ~- ~
heated at the reflux temperature for 8 hours, whilst a stream of -
nitrogen is passed throu~h it. The re~lux temperature rises to 140Co
After the reactlon solution has cooled, the exchanger is filtered
off and excess methoxyisopropanol is distilled off under reduced
pressure. 652 parts o~ methoxyisopropyl carbamate (98~ Or theory,
based on urea) are obtained. The carbamate boils at 92C under 0.2
mm Hg and leaves a distillation residue of only 0.9% by weight.
Melting point - 5~f - 54C.
EXAMPLE 3
C 2H5 0C~2 CH2 0c ONH2
00 parts of urea~ 810 parts o~ ethylglycol and 15 parts o~ a ;~
catlon exchanger which is commercially available under the re-
gistered name Amberlyst 15 and, having been treated in accordanoe `~
with Example la), contains nickel, are heated to the re~lux tempe-
rature (138C) in a stirred vessel. A~ter 2 hours, the re~lux tem-
perature rlses to 148Co 'Ifhe reaction mixture is kept at this tem-
perature ~or a ~urther 8 hours, whilst a slight stream of nitrogen
is passed through it. A~ter ~iltering of'f the exchanger, excess
ethy1glycol is distilled of~ under reduced pressure. 645 parts o~
ethoxyethyl carbamate are obtained4 This corresponds to 97~ of theo- ~f-
ry, based on urea. On distilling the crude carbamate in a high va~
" ~ .
~ cuum~ the end product distils at 110C under O.~f mm Hg. A distilla- ~ f
- 1 1 - ' - '-" ' "
~ a)5 1~ ~'7 0OZ/ 31,037
tion resldue o~ 0, 9% is lef t .
EXAMPLE 4
gOCE~2CH20CONH2
60 parts of urca are mlxed with 177 parts of butylglycol and
3 parts of a cation exchanger which is commercially available under
the registered name Lewatit CA 9259 and, having been treated in
accordance with Example la), contains nickel9 in a stirred appara~
tus~ The mixture is heated to 135Cg whilst stirringO It is then
heated for 10 hours at 140C~ After cooling~ the mixture is fil-
tered and the excess butylglycol is distilled from the filtrate
under reduced pressure. 158 parts of n-butox~ethyl carbamate ~cor-
responding to 98% o~ theory~ based on urea) are obtalned. On distil-
lation of the end product in a high vacuum, a residue of only 0O9
- by weight is le~t. The pure butoxyethyl carbamate has a boillng
point of 118 - 120C at 0O2 mm Hg-
1 ,
, EXAMPLE 5
C4HgcH2cH2cH2cH2ocoNH2 ~ ;
600 parts o~ urea, 2,916 parts Or butyldiglycol and 28 parts of
a cation exchanger which is commercially available under the re-
gistered name Amberlite 200 and, having been treated in acoordance
~ ~ with~Example la), contains nickel, are heated for 10 hours at 150 C
l~ in a stirred vessel, whil:t a slight stream o~ nitrogen is passed
through the mixture. The exchanger is then filtered of~ whilst the
solution is still hot and the excess butyldiglycol is distilled
off under reduced pressure~ 1,988 parts of butyldiglycol carbamate
are obtained. This corresponds to a yield of 97%, based on the
amount of urea employed. The carbamate has a boiling range of 146 -
; 148C at 0.2 mm Hg and leaves a distillation residue of 1O1% by
!; weight~
1~ .,
EXAMPLE 6
4 9 CH2cH2ocH2cH2ocH2cH2ocoNH
A mixture of 120 parts of urea, 741 parts o~ butyltriglycol
and 5 parts of a cation exchanger which is commercially available
-12-
~ ,,
~5~ o.z. ~1J 037
under the registered name Amberllte 200 and~ having been treated
in accordance with Example la)~ contains n~ckel, is heated ~or 10
hours at 145C in a stirred vessel whilst a slight stream of nitro-
gen is passed through the mixture. The exchanger is filtered off
whilst the reaction solution is hot and the excess butyltriglycol
is distilled off under reduced pressureO 493 parts o~ butyltrigly-
; col carbamate are obtained. This corresponds to a yield of 99% of
theory, based on urea. The carbamate has a boiling range of 172-
175C at from 0,? to 0.3 mm Hgo
; EXAMPLE 7
CH 0H -~ H NCONH ~ ~ CH 0C0NH ~ NH
2 2 ~ 2 2 3 ;
A mixture o~ 240 parts of urea, 778 parts of benzyl alcohol
and 11 parts Or a cation exchanger which is commercially available
under the registered name Amberlyst 15 and, havlng been treated in
accordance with Example la) J contains nickel, is heated to the re-
flux temperature (131C) in a stirred vessel. In the course Or 6 ~ -hours, the reflux temperature rises to 149C. The reaction mixture ~-~
is then heated at 149-150C for a further 2 hours. After ~iltering
l off the exchangerJ excess benzyl alcohol ls removed by dlstillation `~
'~ under reduced pressure. 586 parts o~ benzyl carbamate are obtained. ~
; This corresponds to a yield o~ 97~ o~ theoryJ based on urea. Benzyl ~ ;
20 carbamate boils at 116-118C under from 0~3 to 0,4 mm Hg~ Me~lng
polnt = 75 - 76C. On distillation, a residue o~ 1% by weight is
' ~.
le~t. -
j EXAMPLE 8
C6~13CNH2
A mixture of gl8 parts o~ hexyl alcohol, 300 parts o~ urea and
; 14 parts of a cation exchanger which is commercially available under
the registered name Amberlite 200 and, having been treated in ac-
cordance with Example la), contains nickel, i5 heated to 130C whilst
-13-
, .
~:
" ., . - - - . . .. . . . . .. . . ..
:.. . :, . , -.. . .. , ., . , .. ~" . ... " .
_ ~ S ~ 002. 31,037
stirring. The temperature is then ralsed to 150C in the course of
6 hours and maintained thereat ~or a further 4 hours. A~ter fil-
tering orf the exchanger, excess hexyl alcohol is distilled of~ un-
der reduced pressure. 680 parts of hexyl carbamate (94% o~ theory)
are obtained. Melting point - 56 - 57C.
EXAMPLE 9
HOCH2CH2C~I20CONH2
410 parts of 1,~-propanediol, 180 parts Or urea and 11 parts
of a cation exchanger which is commercially available under the re-
gistered name Amberlite 200 andl having been treated in accordance
with Example la), contains nickel, are heated at 150C for 10 hours
in a stirred apparatus, whilst a slighk stream of nitrogen is passed
through the mixture. The exchanger is then filtered o~f and excess
propanedlol is evaporated o~ under reduced pressure. On distilla-
i tion in a high vacuum at l~f8-140C and 0.1 mm Hg~ 350 parts of ~-
1 hydroxypropyl carbamate (98~ o~ theory) are obtained. The distilla-
..j
~i tion in a hlgh vacuum leaves a residue of only 0.9% by weight.
~ EXAMPLE 10
i 17 ~5 NH2
~ ; A mixture of 256 parts Or heptadecyl alcohol, 60 parts of urea
,~ and 5 parts o~ a cation exchanger whlch is commercially available
under the registered name Amberlite 200 and, having been treated
in accordance with Example 1, contains nickel, is heated in a
i 20 stirred vessel to 140-145C9 whilst stirring.A~ter ~iltering Or~ the - -
exchanger whilst the reaction solution is hot, 280 parts of hepta-
decyl carbamate are obtained. This corresponds to a yield of 94%
o~ theory. The product has a melting point of 5~ 5~C. ~;
EXAMPLE 11
~;
NH2 ~
A mixture of 659 parts o~ phenylglycol, 180 parts o~ urea and ;~ ~i
9 parts o~ a cation exchanger which is commercially available under
,:,, ~.,
51~'7
the registered name Amberlys-t 15 and, having been treated in
accordance with Example la), contains nickell is heated to 130C
whilst stirring. The temperature i~ raised to 150C in the
course of 6 hours and i5 then maintained thereat for a further
4 hours. After filtering off the exchanger whilst the reaction
solution is hot, the filtrate is cooled to room temperature.
After standing for several hours, the phenylglycol carbamate
which has precipitated is filtered off. A~ter evaporatin~ of~
the excess phenylglycol under reduced pres~ure, a total of
499 parts of phenylglycol carbamate are obtained. This corre- -~
sponds to a yield of 92% of theory. Melting point = 105-106C.
EXAMPLE 12
CH3 IH3 fH3 1 3
HOCH2-f-COOCH2-C-CH20CONH and H2NCOOCH2-C-COOCH2-C-CH20H
C~I3 ~CH3 CH3 C~I3
612 parts of neopentylglycol hydroxypiralate, 180
parts of urea and 9 parts of a sation exchanger which is ~
commercially available under tbe registered name Amberlite ~ ;
200 and, having been treated in accordance with Example la),
contains nickel, are heated to 130C in a stirred apparatus, ~ `
whilst a slight s~ream of nitrogen is passed through the
mixture. The temperature is raised to 150C in the course of
10 hours. After filtering off the exchanger whilst the reaction
solution is hot, 714 parts of a 1:1 mixture of neopentylglycol
hydroxypivalate carbamate isomers of n20 = 1.4613 are obtained.
Thi~ corresponds to a yield of 96% of theory.
- EXAMPLE 13
H (OCH2cH2)lgOcoN~l2
- 810 part~ of a polyether-diol having the structure
H(OCH2CH2~180H, 60 parts of urea and 3.6 parts of a cation
exchanger which is commercially available under the registered
name Amberlite 200 and, havlng been treated in accordance with
~ 15
~05~017
Example La), contains nickeL, are mixed, and heated to
130C, in a stirred apparatus. The temperature i~ then
raised to 150C in the course of 6 hours and kept thereat for
a further 4 hours. The exchanger is filtered off whilst
'
,
17 o.zO 31,0~7
the reaction solution ls hot~ 805 parts o~ carbamate of the ~ormula
H-40CH2CH2)180CONH2, o~ melting point ~2~ C, are obtained. This
correspond.s to a yi01d Or 94~ Or theory. The product is colorless
and pasty.
EXAMPLE 14
H ~OCH2CH2)90CONH
~14 parts of a polyether-diol having the structure
H-~OCH2CH~)~OH, 60 parts of urea and 4 parts oY a cation exchanger -
which is commeroi~lly a~ailable under the registered name Amberlite
200 and~ having been treated in accordance with Example la), contalns
nickel, are heated to 130C~ The temperature is ralsed to 150C in
10 the course of 6 hours and is then maintained thereat for a rurther ;~
4 hours. After ~ilterlng of~ the exchanger, 415 parts (91% o~ theo~
ry) o~ monocarbamate Or the ~ormula H t0CH2CH2)90CONH2 are obtained.
Refractive index n20 = 1.4708.
EXAMPLE 15 (USE) ` ;;
595 parts o~ the methoxyethyl carbamate manu~aotured accord- .
ing to Example lb), 750 parts o~ a 40 per cent strength b~ wei~ht
formaldehyds solutlon and 6 parts o~ a 50 per cent strength b~ weight
sodium hydroxide solution are heated in a stirred apparatus ~or 3
` hours at 50C, whilst stirrin~. This solution is neutralized with ;
dilute sulfuri¢ a¢id and then made up to 1,790 parts with water.
20 This then constitutes a 50 per cent strength by weight solution o~ ~ ;
dlmethylolmethoxyethyl carbamate.
A bleached and mercerized cotton rabric (poplin) weighing
1~25 g/square meter was lmpregnated~ on a padder, with a solution
prepared by diluting 150 parts o~ a 50 per cent stren~th by weight
aqueous solution of N,N-dimethylolmethox~ethyl carbamate, 1 part of
a reaction product o~ 7 moles o~ ethylene oxide with 1 mole o~ iso-
~; octylphenol and 30 parts of magnesium chloride hexahydrate to 1,000
parts by volume with water. The impregnated fabric is squeezed o~
to a wet pick-up o~ from 70 to 75% and is dried to 6-8% residual
moisture content on a tenter frame at 110C. The treated fabric is
-16-
~ ~:
~05J~7 o. ~ o ~1 ~ 0~7
then heated ~or 4 minutes at 160C on a tenter frameO The technolo- :
gical data are summarized in the Table which follows.
,,
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. :
: 7 ~
.
O.Z. 31,037
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,
rl O O O O OL~ O
h ~d ~ 1 O O O ~ ~:
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V 07 V ~ ~'
o a) o o
W ~1
E .,~
o
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., . o
.j ~ ~ ~ ~ h C~ ~ bO --
~ I ~ 0 ~ 0
cl ~ rl S~ rl
E~ ~ 0 c~ -rl COE q E ~ E
co a) co a) o v
'~ Q E~ I)-r
~ V Z Z V o
~ U~rl
bp ~ I) ~ O~i Orl O ~rl O
rl ~ ~ h O ~1 O h O h O
h ~ X ~ X
C) 1~ C) O O O O ~ O
~ cu 0
0 a~ h (1~ r~
r l r-l ~ r lr~
~ O
~ rl <1) il) 0 a) au ~11
rl ~ ~ h
0 ~ 0 a~ ~ 0 ~ 0
h ~ ~ h h 0r~r-l
O O ,~ C)O ~ rl h ~rrl~ r- r-l : .
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18
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