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Патент USA US2403707

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Patented July 9, ‘1946 ‘
2,403,707 '
if:"UN'ITEDPSTATES PATENT OFFICE" ~
2,403,707,",
-
I PRODUCTION OF ALGmo Aom
Y
‘COMPOUNDS:
;
George Eric Cunningham,'Norman Henry Cham'i ~ " ' ‘
V berlain, and John Bamber Speakman, Leeds,
England, assignors to Cefoil Limited; Maiden-f
head, England, a British company J
.7
i c .
Nov Drawing. Application October 57,711,943, See
rial No. 505,033. In Great'__l$ritain .lulyl,
_
'
V
v1942
'
,
.
rec1aims.'f(o1.2so-209.6)
‘invention comprises improvements -
the,
or I
relating to the production ofjalginic acidlcomé
DQunds.
v
I
j
V
"
' ‘
'
'
‘
'---'I'he'iol1owing are examples of typical proce
V
: “Hitherto, it has been foundv extremely di?lcu-lt
dures inaccordancewiththe invention: -
to‘ prepare“organicmderivatives of'alginic' acid ‘
"
when'simple aqueous media are inadmissible (see,
i011 gexamplee?irst, :JQnes , and. Jones, Jr Ghem,
Soc. 1939, page 1880). ,Theydi?icultyseemsto
arise from the fact that the hydroxyl groups of -
alginic acid are so placed in the long-chain mole
cules that they. are in closeproximity, with there
Vi‘ "
“
Example‘!
"
A
-
V
maize-yard neutron-1,0 gram) oi puri?ed al
ginic acidya'rn is soakedjin'water forlO minutes
or ‘more;7 lightlyrblotted' and ‘treated with'suc
1° cessive 'lotsof glacial acetic‘ acid inv four succes
sive decantations of :30. cubic centimetres each
over a period of not less than one hour.
1 'After drainingfo?urnost of the acetic acid, the '
sultlothati hydrogen bond formation takes place,
alidlthe :compact, structure so obtained .is inac- }
cessible. ,to , or non-reactive with even ‘compara
tively smallmolecules of.--organic reagents.
‘Thef as; results as obtained ‘when
the whole of the'water is'rer'noyed;
specimenisintroduced into"‘20—30 cubic centi_-‘
, 15' metres" ‘of, ‘an acetylating. inixturejcontaining a‘
non-‘solvent,’
5;, According 'tothe present invention, ‘in the pro,
duction of organic derivativespf alginic _acid,~;the '
alginic acid is?rst swollen inan aqueous medium,
the waterlis' thenremovedfrom the swollen struc
.
.
g
follows:
g
"
‘Grams
Acetic anhydride _______________ _.,__j_..__.. ' :j60
Benzene ,.
‘
‘
'
"
';
1%"180
ture, while still maintaining the swollen state,
by ietltqduqinaaa Organic liquid and therm
tions necessary for the'production‘of thedefsired‘
organic deriyatiifefa‘fef theréaftef'caf?eil‘outf‘Ap -‘
(a) The reactionlmay be allowed to proceed for
-1'_772§l~hours at 25° C., and after puri?cation with
. benzenaandether. ctheresulting yarn is white and’
parently‘itheiswelling ofith'e structure in water
lustrous, contains ‘33.0% combined acetyl, and is
leads to separation or: the hydro'xyl groups "of the '25 substantially soluble in aqueous acetone. Yield
chains-'ofpolymerised mannuronic acid-.of which
95-98% vof theory;
‘ , '
_
the'iin'aterial- consists "and when the wateris re
'(b) :A similar product is-obtained if the reaction
moved from the‘ swollen structure byithe organic
is allowed to proceed foi- one hour at 25° (3., fol
liquidfs‘u?ieientseparationof the hydroxyl groups
lowed by a shorter period at a higher temperature
stilljpersi'sts for the subsequent reactions to talre 30 (e. g. l5-30 minutes at _50,—6>0° C.) .’ iv ‘v
place, if necessary in media; containing no water.
.. 1-, .
miniskirt
i
vIAtteIn'pts made? to acetylate alginic acid ac
@One'gram o'fialginic acid‘powderisisoaked in
Y cording tofw‘el-l-known methods, e.fg. those of'
water for 10 minutes or more» and isgthen dehy
Miles, British Patent-No. 19,330 of. 1905; Dreyfus,
French-Patent No.47 8,023 011914;: and Ost._Zeit. 35 drated as described in Example I with successive
changes of glacial acetic-acidf ,
,
'
angewnchems 1919', 32,- 68 wereacomple'tely, un
‘successful with air-dry ' filaments although such
Lilian-treatment with 30' cubic centimetres of V
methods are i known tovbe- successful with ' cel
, lulose.‘ If,'fhowever,1'alginic: acid yarn‘ is soaked
in water for a time to induce swelling, and. the
Water-lthen displaced by glacial acetic ,acid;,rapid
‘acetyla'tioncan be brought ‘about by: acetic. an
itheacetrlati?s reagent? setiqutj in Example I. for
24hours at‘ 25°':C_.,- awhite ‘product, soluble in
40 a‘quéousac,etone, is obtained.
w
H
hydride in‘; presence‘ of.’ a 1 suitable catalyst, e.v g.
* Af'zo-‘yard hank‘ (0,51-1'.0.gram) "or purified 9,1;
sulphuric acid: ‘Therprocesscan be applied to
,ginic acid yarn is soaked'in water for 10 minutes
alginic acidi'in powder, ?lm or?brousvformk . 3.
P‘ . .The alginic acid yarn, soaked in-cwater atjroom
temperature for say two hours, may betreated
45101-1, more, and, is subsequently dehydrated, after
light‘ blotting,'with two successive lots'of 30 cubic
'centim'etres'of absolute‘ methyl alcohol over a
,
‘withzsuccessiveuchanges ,of ‘glacial. acetic acid‘ totalperiqdofpqne hour: ,c
Twenty cubic centimetres of acetylating re
until the‘ quantity. oi?v water retained by thegyarn
less -than~30.%~ on theinltial air-dry weight of , ?o'jagentcontaining benzene, acetic ,anhydride, and
2,403,707
'
4
3
sulphuric acid in the proportions set out in Ex
product is not high (about 5% combined acetyl)
ample I are added. The initial exothermic reac
but it is superior in handle and appearance to
alginic acid yarn,
Example VII
1.5 grams air-dry alginic acid yarn is soaked
tion, which raises the temperature to 60° C., is
controlled by strong cooling, and when the tem
perature has fallen to about 30° C. a further 10
cubic centimetres of reagent is added, and the re
action allowed to proceed for 24 hours at 25-30°
in water for 10 minutes or more, dehydrated with
four successive changes of 50 cubic centimetres
C. The product is substantially diacetyl alginic
glacial acetic acid, and, after draining, is treated
with 50 cubic centimetres of reagent of the fol
acid (34.1% combined acetyl) and is soluble in
aqueous acetone.
lowing composition:
Eccample IV
' I
Grams
6.5 grams air-dry alginic acid yarn is soaked
,
‘
____________________ __' _________ __
180
for 10 minutes or more in a normal solution of
Acetic anhydride _______________________ __
60
sulphuric acid, and dehydrated with four succes
sive changes of 130 cubic centimetres glacial
acetic acid over a period of not less than one
The reaction is allowed to proceed for 48 hours
at 40° 0., when a product containing 10-12%
hour.
7
Benzene
combined acetyl is obtained, which swells highly
in water and which is dispersed by mixtures of
water and acetone.
Example VIII
'
Thus the catalyst is introduced during the pre
soak in water, Most of the catalyst is removed
in subsequent treatment to remove water, prior to
acetylation but sufficient remains to iacilitate the >
1.5 grams air-dry alginic acid yarn is soaked
reaction. This method is valuable in preventing " in Water for 10 minutes or more, dehydrated with
degradation.
.
{our successive changes of 50 cubic centimetres
Acetylation is carried‘ out after draining off
glacial acetic acid and after draining, is treated
most of the acetic acid,"150 cubic centimetres of
the following mixture being used for the purpose:
.
i
Benzene
with 50 cubic centimetresof‘ reagentof the fol
' lowing composition:
Grams
Grams
,
_
w
H
.
139
Acetic anhydride _____g___________________
60 30
‘The, reaction is allowed to proceed for 2a hours
at ‘25° C;, or alternatively, for 1' hour at 25°‘ C.
The reaction is allowed to proceed for 24-hours
at 60“- C;, when a product containing about 16%
followed by 15-30 minutes at 50—60° C. The prod
uctis ‘substantially the diacetyl derivative.
3.5
combined acetyl is obtained.‘
-
>
'
Example IX‘
Example V
A.40-.yard hank of~ puri?ed .alginic. acid yarn
(1.65‘ grams air-dry) is soaked for 10 minutes or
6.5 grams air-dry alginic acid yarn is soaked
more in a» normal solution. of perchloric acid,
for it) minutes or more in a normal solution of
perchloric acid, and dehydrated with four suc 40 drained free from excess moisture, and then- do
cessive changes of 130 cubic centimetres glacial ' 1 hydrated‘ With four successive changes of 50 cubic
centimetres of glacial acetic acid over a. period
acetic acid over a period of not less than one
hour;
of one hour-or» more. ' Excess acetic acid .is
,
drained. o?, and the material treated with the fol
lowing mixture at 60°. C.v for 30.. minutes:
,Acetyl'ation maybe carried out after draining
o? most’of the acetic acid, 150 cubic centimetres
of the following mixture being used for the pur
i
‘
or
_
I
Grams.
I Propioni'c anhydride ____;__.:_____.._~___‘____.-._ 12
'Grams
Benzene
_
_ -
__
Benzene
Acetic anhyd-ride ___..._;_..__----_-__--.._.____
60 50
at 25°C., followed‘ by 15-30 minutes at 50P—.60° C.
tive.
.
a
,
'
'
>
-
36
lustrous yarn which may be heated to, at least
60° C. without discolouration,isfseluble in, aqueous
The reaction is allowed to proceed for from
2-24 hours at 25° C., or alternatively, for one hour
The, productlis substantially the diacetyl’ deriva
‘
,The product ispuri?ed with benzene and ether
to. remove traces, oi the rea‘gent._ ,Itis a white
180
acetone
substantially
and in
composed
benzeneahachok
ofdinropi0ny1‘a1sinic
mixtures. and
acid
55 010% propionyb. The. yield is: 92%. oithat theo
This example is like Example IV, except that
retically obtainable,_
_
‘a
‘
perchloric acid is used as the catalyst. Perchloric
‘a The above Examples .VI,
acid could be; used in. all the: above examples. in
processes where no catalyst: isemployed.
In Example III it will be. noted that; methyl a1,
place of, sulphuric acid.
‘
> -
and VIIIIare _ of '
cohol. is used to displace water instead of _ glacial
‘ Egwmnze VI
acetic acid,-.-.‘Other organic liquids may, beused
" 125' grams or" air-dry’ alginic acid yarn is soaked
in water fonlq'minutes or more, dehydrated with
four successive ‘changes ‘of 50 cubic vcentimetres
glacial acetic acid, and'after draining is treated
with 50 cubic centimetres of reagent containing
acetic anhydride and benzene, (but no catalyst)
inthe, following proportions:
Grams
Benzene j_'_'____ _
,
____
t
Acetic anhydride ____________________ __g___
180
60
for the'purpose; providing they are su?icientlll
polar-.to-rprevent re-association. of the hydroxyl
» groups of the aIginicacidwhen-othe waterisrce
65
movecly
..~
,,
r.
.
.l
-
l
,
7 Moreover-,- instead of displacing water: from the
swollen .alginic acid by means. oi'glacialjacetic
acid or methyl alcohol; it: could, be removed by
combination; thus, acetic anhydride could. be
10V added, with cooling;to..,water-swollen. or; sul
phuric-acid+solutioneswollen ,j alginic'v ' acid”: The
water would thus be removed by combination
with acetic anhydride to form. glacial acetic acid.
The reaction is allowed‘ to proceed for-‘one week
Finally the-principles described.- above. may be
at 20-25° C.‘ and the product‘ puri?ed with ben~~
acne and ether. The degree of acetylation of the 7.5 applied in; the preparation of other esters/(the
2,403,707
5
butyrate, for example) and mixed esters (the
aceto-butyrate, for example).
We claim:
7
1. In the production of lower fatty acid esters
of alginic acid, the steps ‘of ?rst swelling the
alginic acid in an aqueous medium for at least
'ten minutes, then removing water from the
swollen structure, while still maintaining the
a. A process as claimed in claim 1 wherein the
reaction of the alginic acid, after swelling, is
facilitated by the presence of a catalyst in the
reaction mixture.
‘ ’
5. A process as claimed in claim 1, whereina
catalyst is introduced as an ingredient of the
aqueous swelling medium.
6. In the production of lower fatty acid esters
of alginic acid, the steps of ?rst swelling the
swollen state, by introducing an hydrophyllic
organic liquid which is su?iciently polar to pre 10 alginic acid in an aqueous medium, then remov
ing water from the swollen structure while still
vent re-association of the hydroxyl groups of the '
maintaining the swollen state, by introducing a
alginic acid when the water is removed,‘ and there
hydrophyllic organic liquid of the class consisting
after carrying out the reactions necessary. for the
of lower fatty acids and their anhydrides which
production of the desired lower fatty acid esters.
2. A process as claimed in claim 1 wherein the 15 is ,suf?ciently polar to prevent re-association of
the hydroxyl groups of the alginic acid when the
Water is removed by displacement with glacial
water is removed, and thereafter carrying out
acetic acid.
' I
the reactions necessary for the production of the
3. A process comprising the steps set forth in
desired lower fatty acid esters.
claim 1 wherein removal of the water is effected
by causing it to combine with an hydrophyllic 20
organic liquid which is introduced into the reac
tion mixture, said hydrophyllic organic liquid
being sufficiently polar to prevent'reassociation
of the hydroxyl groups of the alginic acid when
the water is removed.
GEORGE ERIC CUNNINGHAM.
NORMAN HENRY CHAMBERLAIN.
JOHN BAMBER SPEAKMAN.
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