close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2407001

код для вставки
Patented Sept. 3, 1946
2,407,001
UNITED STATES PATENT OFFICE
SUGAR DERIVATIVES
William C. Gri?in, Tamaqua, Pa., assignor to
‘Atlas Powder Company, Wilmington, Del., a
corporation of Delaware
No Drawing. Application July 16, 1943,
Serial No. 494,973‘
17 Claims. (01.‘260-209)
1
2
The present invention relates to improvements
in sugar derivatives and compositions containing
the same.
col, about 9 to 15% reducing sugar remains when
equilibrium isreached.
The. reaction product is preferably treated by
neutralizing the. acidic catalyst by means of suit
'
An object of the invention is to provide a
process for making sugar derivatives and compel 5' E able alkalinematerials, and any precipitate re
‘
sulting therefrom is subsequently removed, as by
Another object of the inventionv is to provide
decantation or‘?ltration. Any soluble ions may
new compositions of sugar derivatives;
_
be .removed'by the customary procedures, for
Other objects will become apparent in the
example, treatment with ion-exchangers, selec
sitions containing them.
course of the following description.
tiveadsorbents and the like. If necessary, the
product can be further treated with bleaching
agents or decolorizing carbon to improve the
color if substantial darkening has occurred in
In- accordance with the present invention, it
has been found that sugars containing from 5-to
6 carbon atoms can be reacted with glycols with
2 to 3 carbon atoms and the 'dihydric inter-ethers
thereof with’ not more than 6 carbon atoms in
the-presence of strong ‘mineral acid condensing
agents and at elevated temperatures to produce
novel and useful compositions. Suitable sugars
for the process are, for example, glucose, fruc
tose, galactose, inverted sucrose, and xylose.
the reaction. , These purifying steps are not gen
erally required, however, because the reaction
product ‘will ‘be found suitable directly for most
applications.
It is further possible to treat the product to
remove the residual sugar.
A suitable step for
20 accomplishing this purpose is selective fermenta
Suitable gylcols‘include ethylene glycol, di-ethyl
tion of the sugar.
The reaction product is a viscous, water-solu
ene glycol, tri-ethylene’ glycol, propylene glycols,
di-propylene glycols, and hydroxy ethyl ethers
ble, hygroscopic liquid.
This composition has
of propylene glycols. Suitable catalysts are the
strong mineral acids such as sulphuric acid,‘ hy
been found useful as a plasticizing and condition
drochloric acid, iodine (which decomposes to give
‘ glue printroll compositions, and cork glue com
ing .agent for the preparation‘ of ?exible glues,
iodine acids in the reaction) and aryl sulphonic
acids. Of these catalysts, sulph'urlc "acid is pre
ferred.
‘
‘
p
or
,
positions.
.
The reaction is conducted by mixingapprox
imately equimolecular proportions of the sugar
to
and glycol and a small amount, for example 0.03
Other uses for the material are the
conditioning of cellulosic materials in the form
of sheets, ?lms, threads, or the like. It is also
useful as a conditioning agent for tobacco, gela
tine products and other hydrophilic materials
with which it can be incorporated.
to 0.2% of the catalyst, based on the total weight
' The ‘composition also is useful as a polyhydric
of the sugar and glycol. The reactants are heat
material for the preparation of chemical deriva
ed to a temperature su?icient to cause the re 35 tives such as esters, ethers, acetals and the like.
action mixture to clear and not over about 140°
‘The following examples illustrate typical proc
C., under a re?ux condenser or in a closed vessel
esses and compositions according to the inven
which prevents the escape of volatile reactants
tion.
‘
and reaction products. In the case of most of
Example I -
the reaction mixtures, the clearing temperature
1801parts by weight glucose (1 mol), and 83.6
is in the neighborhood of 120° C. Lower tem
parts by weight propylene glycol (1.1 mols), were
peratures can be employed, but it has been found
placed together in a reaction vessel to which was
that better products can be made and the process
attached a re?uxcondenser. The mixture was
is more practical at the preferred operating tem
peratures. The catalyst can be added to the 45 heated to the clearing temperature of about 120°
C. and 0.05% iodine (based on total charge)
glycol or glycol ether and the sugar thereafter
was added. , Thereafter, the temperature was
added to the solution. Preferably, however, the
sugar and glycol or glycol ether are mixed to
gether and‘ heated until the mixture clears and
then the catalyst is added.
‘
1
Under these operating conditions, the reaction
comes to an equilibrium‘in which a minor-por
raised to 130° C. The reaction proceeded rapidly
with the evolution of water which was returned
to. the vessel from the re?ux condenser. At the
50 end of the reaction, the product was found to
contain 12.8% reducing sugar. Water was added
tion of reducing sugar remains as indicated by a
test, for example, with Fehling’s solution. ‘ In the.
case of glucose and propylene or di-e‘thylene gly 55
to the product to bring the water content to 15%.
At'25° C. the composition, containing 15% water,
was amber colored and“ had a viscosity of 5900
centipolses.
‘
2,407,001
_"
.1
. "
4
3
Example II
180 parts by weight glucose (1 mol), and 83.6
containing from 5 to 6 carbon atoms and a com
parts by weight propylene glycol (1.1 mols) , were
placed together in a reaction vessel to which was
pound of the class consisting of glycols with 2 to
3 carbon atoms and the dihydric inter-ethers of
said glycols with not more than 6 carbon atoms,
in substantially equimolecular proportions, in the
attached a re?ux condenser.
presence of a strong mineral acid catalyst, at a
The mixture was
heated to the clearing temperature (about 120°
C.) and 0.05% concentrated H2804. (based on
total charge) added in the form of a 50% aqueous
solution. Thereafter, the temperature was raised
to 130° C. and held at that value for 60 minutes. ~
The reaction proceeded vigorously with the evo
temperature of substantially 120 to 140° C., under
re?uxing conditions in which the volatile react
ants and volatile reaction products are returned
to the reaction mixture, and continuing the reac
tion substantially to equilibrium.
3. A- process for producing sugar derivatives
whichcomprises mixing a sugar containing from
'
5 to 6 carbon atoms with a compound of the class
product contained 13.8% reducible sugar. The ‘
consisting of glycols with 2 to 3 carbon atoms and
water content was adjusted to 17.9%. Thereafter,
, the dihydric inter-ethers of said glycols with not
0.08% NaHCOa was added to neutralize the acid ~
morethan 6 carbon atoms, in substantially equi
lution of water which was returned to the reac
tion mixture from the reflux condenser, The
catalyst.
The product was of light amber color. .
molecular proportions, heating said mixture to the
and ‘had a viscosity at 25° C. of 2120 centipoises. , ‘ clearing temperature to form a clear solution,
Example III
20 adding a catalytic amount of a strong mineral
acid to the clear solution, and reacting the sugar
180 parts by weight glucose (1 mol), and 116.6
parts by weight diethylene glycol (1.1 mols) , were
placed together in a reaction vessel to which was
attached a re?ux condenser. The mixture was
and said compound to substantialequilibriumin
the presence of said acid and under conditions in
which volatile reactants and volatile reaction
products are retained in the reaction mixture.
heated to the clearing temperature of about 120° 25
4. A process for producing sugar derivatives
C. and 0.04% iodine (based on total charge) Was
which comprises mixing a sugar containing from
added. The temperature was then raised to 125°
5 to 6 carbon atoms with a compound of the class
C. and held at that value for 60 minutes. The
consisting
of glycols with 2 to 3 carbon atoms
reaction product, which contained 14.2% reducing
and the dihydric inter-ethers of said glycols with
sugar, was diluted with water to bring the water
not more than 6 carbon atoms, in substantially
content to 11.6%. The solution was amber in
equimolecular proportions, heating said mixture
color and had a viscosity at 25° C. of 6470 centi
to the clearing temperature to form a clear solu
poises.
tion, adding to the clear solution from 0.03 to
If it is desired to obtain products of lighter
0.2% of sulphuric acid based on the total charge.
35
color, the reaction product can be treated with
and reacting the sugar and said compound to
activated carbon or the like, preferably after
substantial equilibrium at a temperature not ex
diluting with water to a more readily ?lterable
ceeding 140° C. in the presence of said acid and
viscosity.
It will be noted that in the examples a 10% 40 under conditions in which volatile reactants and
volatile reaction products are retained in the re
excess of glycol over the equimolecular amount
action mixture.
_
is employed. This is not essential but has been
, 5. A process which comprises heating glucose
found to facilitate the preparation of the products
and a compound of the class consisting of glycols
and to compensate for side reactions involving
with 2rto;.3 carbon atoms and the dihydric inter
the glycol or glycol ether alone.
45 ethers of said glycols with not more than, 6 car
The products of these examples are non-crys- I
bon atoms, in substantially equimolecular pro
tallizing liquids which are soluble in water and
portions inltlhe presence of a strong mineral acid
in hydrophile solvents. They can be used directly
catalyst,_said-heating being conducted at a tem
for many conditioning or humectant applications.
perature su?icient to cause the reaction mixture
The chemical composition of the reaction prod
to clear and not over about 140° C. and, under
ucts is not de?nitely known, but they are believed
conditions in which the volatile reactant and
to contain a mixture of the isomeric glycol or
volatile reaction products are retained within the
glycol ether glucosides of the sugar employed to
reaction mixture, and continuing the heating
gether with sugar self-condensation products,
until the reaction substantially reaches equilib
The other products of the invention, namely 55 rium.
‘
those made from the other glycols or glycol ethers
6. A process which comprises heating glucose
and sugars, can be prepared by processes similar
and propylene glycol in substantially equimolec
to the foregoing.
ular proportions in the presence of a strong min
What is claimed is:
_
eral acid catalyst, said heating being conducted
1. A process for producing sugar derivatives 60 at a temperature sufficient to cause the reaction
mixture to clear and not over about 140° C. and
which comprises heating a sugar containing from
under conditions in which the volatile reactant
5 to 6 carbon atoms with a compound of the class
and volatile reaction products are retained in the
consisting of glycols with 2 to 3 carbon atoms and
reaction mixture, until the product‘ contains not
the dihydric inter-ethers of said glycols with not
more than 6 carbon atoms, in substantially equi 65 more than about 15% reducing sugar.
7. A process as in claim 4 wherein the ‘said
molecular proportions, in the presence of a strong
sugar is glucose and the said compound is propyle
mineral acid catalyst, said heating being con
ducted at a temperature sufficient to cause the
ene glycol,
.
-
j
-
-
j
>
'
~
8. Aprocess which comprisesheating glucose
reaction mixture to clear and not over. about
140° C. and under conditions in which volatile 7.0. with di-ethylene glycol in substantially equi
molecular proportions in the presence‘ of a strong
reactants and volatile reaction products are re
mineral acid catalyst, said- heating being con
tained in the reaction mixture, and continuing
ducted at a temperature suf?cient'to cause the
the heating until the reaction substantially
reaction mixture to clear and not over about
reaches equilibrium.
2. A process which comprises reacting, a sugar
140° ‘C. and under conditions in which the volatile
2,407,001
reactant and volatile reaction products are re
tained in the reaction mixture, until the reaction ‘
product contains not more than about 15% re
ducing sugar.
7
9. A process as in claim 4 wherein the said
sugar is glucose and the said compound is di
ethylene glycol.
10. As a new composition the reaction product
produced ‘by the process of claim 1.
6
adding a catalytic amount of a strong mineral
acid to the solution, reacting the glucose and
propylene glycol at from 120 to 140° C. under
re?uxing conditions until the product contains
not more than about 15% reducing sugar, and
adding an alkaline material to the product to
neutralize the catalyst.
15. A composition comprising the reaction
product produced by the process of claim 14.
11. As a new composition the reaction product 10
16. A process for producing sugar derivatives
produced by the process of claim 5, said com
position being a viscous, water-soluble, hygro
which comprises mixing glucose and diethylene
glycol in substantially equimolecular proportions,
scopic liquid.
heating said mixture to form a clear solution,
adding a catalytic amount of a strong mineral
12. A composition comprising the reaction
product produced by the process of claim 6, said 15 acid to the solution, reacting the glucose and di
ethylene glycol at from 120 to 140° C. under re
composition being a viscous, water-soluble, hygro
?uxing conditions until the product contains
scopic liquid.
'
not more than about 15% reducing sugar, add
13. A composition comprising the reaction
ing an alkaline material to the product to neu
product produced by the process of claim 8.
14. A process 'for producing sugar derivatives 20 tralize the catalyst.
1'7. A composition comprising the reaction
which comprises mixing glucose and propylene
product produced by the process of claim 16.
glycol in substantially equimolecular proportions,
heating said mixture to form a clear solution,
‘
WILLIAM C. GRIFFIN.
Документ
Категория
Без категории
Просмотров
0
Размер файла
422 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа