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Патент USA US3086981

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United States Patent 0 " ice
3,085,971.
Patented Apr. 23, 1963
2
1
consisting of a chemical oxidizing agent and of a chemical
'
reducing agent is added. A catalytic mixture, consisting
of potassium persulfate (K2S2O8) as the oxidizing agent,
3,086,971
PROCESS OF CRQSS-LIG STARCH WETH
HEXAHYDRO - 1,3,5 - TRIS - ACRYLYL - s - TRI
is very satisfactory and may be added in quantities such
AZiNE.
that the quantity of potassium persulfate (KzSzOs') ap
pnoximates 0.010-0.040% of the dry substance weight of
Donaid'l‘rimnell, Granite City, Ill., Chiin P. Patel, St.
Louis, Mo., and Jack F. Johnston, Granite City, lib,
assignors, ‘by 'mesne' assignments, to Union Starch &
Re?ning Co., Inc, Columbus, Ind, a corporation of
Indiana
No Drawing. Filed Sept. 29,1959, Ser. No. 843,063
4 Claims. (onto-233.3)
The present invention relates generally to starch deriv
the starch in the slurry and the quantity of sodium bi
sul?te (NaHSO3) approximates 0~0.015% of the dry sub
stance weight of the starch in the slurry. (When potas
10 sium 'persulfate is added as the oxidizing :agent'no re
atives, and more particularly to new high viscosity water
ducing agent is required.) Subsequently, a quantity of
the reactant, henahydro-l,3,S-tris-acrylyl-s-triazine, for
example, ‘about 0.02-0.20% of the ‘dry substance weight
soluble starch products, and to a new method for pro
of starch in the starch slurry, is added in the form of a
ing agent.
substituted for the potassium persul?ate.
ducing such derivatives from starch. Speci?cally, the 15 dispersion in water. Other om'dizing agents, for ex
ample, the alkali metal and ammonium persulfates, per
present invention pertains to thick and thick-thick boil
manganates, bromates, chlorates ‘and dichromates may be
ing starches obtained by reacting starch with a cross link
The mixture is then allowed to react at the selected pH
vide new thick and thick-thick boiling starches and a 20 (between 4 and 6) for a controlled time, between one
half to seven hours, whereby the cross-linking of the
new method of producing the same, especially from un
starch chains takes place through the reaction of the three
modi?ed starch. More particularly it is an object to pro
Among the objects of the present invention is to pro
so-called “active centers” of each hexahydro-l,3,5-tris
vide thick and thick-thick boiling starches which are
acrylyl-s-triazine molecule.
maintained at a substantially constantviscosity during
The process is especially suited \for the treatment of
long periods of cooking, and a new method for producing 25
unmodi?ed corn starches but is ‘also suitable for thepro~
the same, especially from unmodi?ed starch (such as
duction of high viscosity starches from other starches
obtained from corn).
such as wheat, rice, sorghum, potato, oat, arrowroot and
Thisinvention is based on the discovery that new thick
barley starches. The treatment as it is applied to un
‘and thick-thick boiling starches can be produced from
starch, by reaction with hexahydro-l,3,5-tris-acrylyl-s-tri 30 modi?ed starches is preferred because it eliminates the
necessity of a pretreatment to produce the modi?ed
azine in the presence of a catalyst. The said triazine
starch; however, the treatment of starches which have
compound‘h'as three-“active centers” whereby each mole
been modi?ed is not precluded.
culeof hexahydro-l,3,5-tris-acrylyl-s-triazine- can theoa
Examples of variables that may be manipulated or
retically undergo polymerization at three different sites
in the presence of a suitable catalytic system and/ or can
react with the starch granule to form a maximum of
three cross-linked starch chains per molecule of said hex-a
hydro-1,3,S-tris-acrylyl-s-triazine employed.
Brie?y, the present invention comprises reacting a rela
tively small amount of hexahydro-1,3,5-tris-acrylyl-s-tri
azine with starch, especially unmodi?ed starch (as ob
tained from corn). The conditions which aliect the
reaction, more or less, are the pH, time, temperature,
catalyst composition and concentration, Baumé of starch
controlled to regulate the reaction and the type of re
sultant, product, include, the concentration of hexahydro
1,3,S-tris-acrylyl-s-triazine, the nature and concentration
of the catalytic system, the pH, the temperature of the
reaction, and the time ofreaction. Themost sensitive
40 of these variables appear to be pH, the nature and con
centrationof the catalytic system, and the concentration
of the hexahydro-l,3,5-tris~acrylyl-s_triazine. When these
variables are predetermined the time of reaction is not
too critical, as will be shown by results using the C.I.V.
slurry, and concentration of tri-functional monomer.
In following the teachings of the present invention, a
starch slurry, for example, unmodi?edcorn starch gran
ules'and water,- at a temperature of about ‘90°'¢-130° F.
(Corn Industries’ viscometer), indicating that the reac
tionis substantially complete after one-halt hour through
about 4 to 6. The starting pH of the slurry is usually in
the neighborhood of about 3-5 and will depend upon
the starch slurry Within the range speci?ed appearsto
the constancy of results obtained in the‘ interval ofone- .
half to seven hours. The temperature should be between
about 90° F. :and 130"~F. However, the best visoosities
and with a Baurné of 20~22° Bé., is treated with a base
orvacid‘t-o adjust the pH ‘thereof to preferably between 50 are obtained at the higher temperatures. The ° Bé. of
the source of the corn, the time of the year, and con
have no in?uence upon the extent of the reaction.
By controlling the main variables, a starch can be
ditions in the plant which produces the slurry. Any base
produced which, upon cooking, provides a relatively low
reactant and catalytic system and the reaction cycle. The
density of the slurry is not unduly critical and may range
‘example, a relatively high viscosity thick-thick boiling
from about 17° to about 24° Ba-urné; this is the pre
ferred range of Bé. of slurries as they come from the
duced by the cross-linking of the hexahydro-l,3,5-tris~
acrylyl-s-triazine polymer and the starch chains increase
or acid may be used which will adjust the pH to asuit 55 viscosity‘thick boiling starch, ‘or a relatively high vis
cosity thick-thick boiling starch. For example, if a rela
able level, such as sodium carbonate (Na2CO3), hydro
gen chloride (HCl), or the like. It shouldbebornein
tively very small amount (for example 0.025 to 0.050%)
mind that the base or acid, per so, does not’react'to
of reactant is used, the resultant product produces a thick
“modify” the starch, but instead only adjusts the pH of
boiling starch of relatively low viscosity. If the amount
60
the slurry to prepare the latter for the addition of the
of reactant is increased to about 0.075 to 0.200%, for
conventional commercial equipment.
After the slurry has been adjusted to a suitable pH,
speci?cally to between pH 4 and 6, a catalytic mixture
starch results.
It is suspected that the aggregates pro
in size, and help to produce a more viscous starch.
After the reaction, the resultant product can be di
3,086,971
3
4
luted with water to approximately. 17 degrees Baurné,
?ltered, dried ‘and packaged.
The ‘following examples further illustrate the method
tris~acrylyl-s-triazine for 3 hours at pH 5.0 and 110° F.
using 0.017% of a 1:1 mixture of potassium persulfate
and sodium lbisul?te. The results indicate that the C.I.V.
of carrying out the invention and are also tabulated to
show the effect on the viscosity of the resultant starch
maxima were increased 20-70 gram centimeters over the
controls.
product of various amounts of hexahydro- 1,3,5 -tris
acrylyl-s-triazine, of di?erent pH values, of time, of tem
Example 9-14
These examples‘ show the effect of varying the con
centration and ratio of potassium persulfate:sodium bi
perature, and of the concentration and nature of the
catalytic system, series of runs were made varying the
amount of hexahydro-1,3,5-tris-acrylyl-s-triazine ‘between 10 sul?te catalyst upon the reaction of hexahydro-1,3,5-tris—
acrylyl-s-triazine within starch.
0.02 and 0.20% of the dry substance weight of starch
in the 'slurry, varying the pH of the starch slurry be
tween 3 ‘and 7, varying the time of reaction between 1
and 7 hours, varying the temperature between 110° and
120° F, and varying the concentration of potassium per 15
Total
concen
Ex.
N0.
sulfate between 0.010 and 0.040% and sodium bisul?te
tration
of cata
lyst, per
cent
between zero and 0.015% of the dry substance weight
of starch in the catalyst. It has been found that potas
sium persulfate has the ability to catalyze the reaction
when used alone. However, the reaction is improved
when sodium bisul?te is added in addition to the potas
0. 015
0. 020
0. 025
20 12
13___.
Example 1
tion of po~ Ratios
tassiurn of cata
persulfate
alone, per
lyst
Determinations
Controls
C.I.V. C.I.V.
C.I.V. C.I.V.
maxi
cent
30 min.
30 min.
max.
0. 0075
0. 015
0. 025
0. 025
14____
sium persulfate.
Concentra
In Examples 9-14, a starch slurry of 23-24“ Bé. was
A corn starch slurry of about 22° Bé. and about 115°
reacted with 0.10% of hexahydro-1,3,5-tris-acrylyl-s
F. was provided, and sodium carbonate added to raise 25 triazine for 3 hours at pH 5.0 and 110° F. in the pres
the pH to 5.0. A quantity of hexahydro- 1,3,5 -tris
acrylyl-s-triazine equivalent to about 0.1% of the dry
substance weight of starch in the slurry was mixed with
ence of the speci?ed amount of catalyst. From these
results it appears that the 1:1 catalyst is superior to the
3:1 catalyst, and that a minimum catalyst concentration
Water and added to the slurry. At the same time a quan
equivalent to 0.01% of potassium persulfate is neces
30
tity of potassium persulfate equivalent to 0.0125% and
sary to increase the viscosity. The potassium persulfate
of sodium bisul?te equivalent to 0.0125% of the dry
alone (Example 12) is capable of causing a large in
substance weight of starch in the slurry was added di
crease in the viscosity at 0.015%.
rectly in the ‘granular form. When these substances were
mixed therein, a reaction occurred which caused the pH
Determinations
Controls
level to drop to 4.5 after one hour, and the pH was 35 Ex. Temp., °
No.
F.
then returned to the selected level of 5.0 by the addi
C.I.V.
C.I.V.
C.I.V.
tion of powdered sodium carbonate. Subsequently the
Max.
30 min.
Max.
C.I.V.
30 min.
starch slurry was diluted to about 17° Bé. with hot water,
raising the temperature of the slurry to 120—125° F.
During the next hour the slurry was ?ltered, sent to the
15____
16--.
110
120
22-23 : 17
22-23 2 1 7
210
191
195
175
156
145
135
118
drier, and ?nally packaged.
It is well known that the viscosity of different batches
In Examples 15 and 16, a starch slurry of 22—23° B6.
was reacted at the temperature speci?ed with ‘0.1% hexa
of unmodi?ed pearl starch, when cooked, is not uniform,
primarily because of the variations in the characteristics
of the corn used in producing it, and the conditions of 45
manufacture. Therefore, for the comparisons made in
hydro-1,3,S-tris-acrylyl-s-triazine and 0.025% of 1:1 p0
tassium persulfate-sodium bisul?te catalyst for 3 hours at
pH 5.0 and subsequently diluted to 17° Be. prior to ?l
the following examples it was necessary to use “control”
tration.
From these results it may be seen that dilution
of the slurry to a lower ° Bé. did not affect the increase
starch of determined viscosity to measure the change in
viscosity caused in the modi?ed starch through the dif 50 in viscosity obtained at the higher’0 Bé., even when the
temperature was varied between 110—120° F.
ferent variables. In measuring the viscosities of both the
unmodi?ed “contro ” starches and the modi?ed or treated
Examples 17-23
These examples show the effect of varying the pH of
ter was used.
In all of the following examples, all of the C.I.V. runs 55 starch slurry in the reaction of hexahydro-l,3,5-tris
acrylyl-s-triazine with starch.
were made at 5.0% concentration of starch on the dry
starches, a ‘Corn Industries Research Foundation viscome
substance basis:
Examples 2~8
Effect of varying the concentration of hexahydro-1,3,5
tris-acrylyl-s-triazine upon the C.I.V. of starch.
Concentration
5-tris-acryly1»s
Example ofhexahydro-1,3,
No.
Determinations
C.I.V.
C.I.V.
C.I.V.
C.I.V.
Max.
30 min
Max.
30 min.
1 0. 025% of the same catalyst used.
155
175
187
178
205
192
204
Controls
pH
C.I.V.
C.I.V.
max.
30 min.
C.I.V.
30 min.
Controls
cent
170
192
196
193
225
205
218
No.
60
triazine, per-
0. 025
0. 050
0. 075
0. 100
0. 125
0.150
0. 200
Determinations
Example
148
148
155
150
155
147
137
145
135
145
140
1 117
148
137
In Examples 17-23, a starch slurry of about 23° Bé.
was reacted with 0.1% hexahydro-1,3,5-tris-acrylyl-s-tri~
azine and 0.025% of 1:1 potassium persulfate-sodium
bisul?te catalyst for 3 hours at 110° F. at the pH speci
?ed. All controls were determined at pH 5.0. From
these results it may be seen that there were viscosity in_
In Examples 2—8, a starch slurry of 23-24" Bé. Was
creases only between pI-I’s 4.0_6.0, with the greatest in
reacted with the speci?ed amount of hexahydro-1,3,S 75 creases at 5.0 and 5.5.
6
5
dichromate. Potassium bromate requires work at con
centrations of at least about 0.05%. Potassium dichro
mate was least satisfactory, because of 30 minute insta
Examples 24-30
These examples show the e?ect of varying the reaction
time of hexahydro-1,3,5-tris~acrylyl-s-triazine with starch.
Determinations
bility and high age paste viscosity, and also because of a
reduction of the dichromate to chromic ion, causing a
green discoloration in the starch. However, all of these
Controls
Time in
Example No.
hours
1
2
3
4
5
6
7
oxidizing agents do have a catalyzing effect.
O.I.V.
0.1.V.
0.1.V.
O.I.V.
max.
30 min
max.
30 min.
192
192
191
191
190
190
191
182
180
179
184
180
177
178
145
145
145
145
145
145
145
It is to be understood that the foregoing descriptions
have been given only by way of illustration and example,
10 and that changes and alterations in the present disclosure,
which will be readily apparent to one skilled in the art,
118
118
118
118
118
118
118
are contemplated as within the scope of the present in
vention, which is limited only by the claims which fol
low.
,-
I claim:
1. The process of making a starch derivative which
In Examples 24-30, four liters of starch slurry of
when cooked provides a dispersion of increased viscosity
about 23° Bé. were reacted with 0.1% hexahydro-l,3,5
over the original starch comprising providing a starch
tris-acrylyl-s-triazine and 0.025% of 1:1 potassium per
slurry at a pH of between about 4 and 6 and at a tem
sulfate-sodium bisul?te catalyst at pH 5.0 and 110° F. 20 perature between about 90° F. and about 130° F., react
for the time speci?ed. At the end of each hour aliquots
ing said starch with between about 0.02 and about 0.20
of 500 ml. were determined. From these results it may
of the dry substance weight of starch of hexahydro-1,3,5
be seen that the reaction was complete by the ?rst hour
tris-acrylyl-s-triazine in the presence of a substantially
and changed little subsequently.
neutral oxidizing type of catalyst, and then ?ltering and
Examples 31-37
5 drying the resultant product.
2. The process as claimed in claim 1 wherein the
These examples illustrate the effects of various other
catalyst is an oxidizing-reducing type of catalyst.
oxidizing agents.
Determinations
Exam
1e
Nap
Type 0 i
oxidant,
Lei“?
oxi an ,
percent
565%‘
a
a,
percent
p
H
0.1.V.
O.I.V.
max. 30 min.
Controls
APV
0.0125
0.0125
5.0
180
163
0.0125
0.0125
5. 0
192
180
0.025
0.025
5.0
180
160
1, 120
0. 025
0.025
5.0
185
165
880
0.025
0. 05
0 05
0.025
0. 05
0.05
5. 0
5. 0
5.0
190
173
193
187
122
180
600
1, 360
0
6
______ ._
In Examples 31-33 the potassium permanganate was 40
added in an aqueous solution apart from the sodium bi
0.1.V.
C.I._V.
max. 30 mm.
APV
160
145 ______ __
100
145
1,176
151
142
______ __
161 ______________ __
140
155
155
130
138
138
1, 016
1, 320
1,320
3. The process as claimed in claim 1 wherein the
catalyst comprises about 0.01% to about 0.05% of po
tassium persulfate and up to 0.015% of ‘sodium bisul?te.
sul?te.
4. The process as claimed in claim 1 wherein the starch
In Examples 31 and 33 the permanganate was added
slurry provided is a corn starch slurry of between about
?rst, and in the Example 32 the bisul?te was added ?rst.
Subsequent determinations indicated the order of addition 45 17° Bé. and about 24° Bé.
was unimportant.
In the Examples 34-37 the oxidant and the sodium
bisul?te were added together in solid form. Of these,
the ammonium persulfate gave the ‘best results followed
References Cited in the ?le of this patent
UNITED STATES PATENTS
by potassium bromate, potassium chlorate, and potassium 50 2,910,467
Wimmer ____________ __ Oct. 27, 1959
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