CA1185405A - Stabilized, polysaccharide-thickened aqueous solutions - Google Patents
Stabilized, polysaccharide-thickened aqueous solutionsInfo
- Publication number
- CA1185405A CA1185405A CA000425914A CA425914A CA1185405A CA 1185405 A CA1185405 A CA 1185405A CA 000425914 A CA000425914 A CA 000425914A CA 425914 A CA425914 A CA 425914A CA 1185405 A CA1185405 A CA 1185405A
- Authority
- CA
- Canada
- Prior art keywords
- polysaccharide
- sulphur
- thickened
- atom
- aqueous solutions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/40—Thiurams, i.e. compounds containing groups
Abstract
Abstract Stabilized, Polysaccharide-thickened Aqueous Solutions A means is provided for stabilizing polysaccharide-thickened aqueous solutions by including in the thickened solution from .01% to 1% w/w of a thiuram sulphide or thiomorpholine compound as stabilizer. These stabilizers provide improved resistance against breakdown of the gels and separation of the gel ingredients particularly when the gels are exposed to elevated temperatures. The invention has application in the fields of paints, pharmaceuticals, printing, explosives or wherever polysaccharide-thickened aqueous solutions are employed.
Description
This invention relates to aqueous solutions or dispersions which are thickened or gelled by means of water soluble polysaccharides. In particular, the invention pro~ides polysaccharide-thickened aqueous solutions which have improved stability, especially at elevated temperaturesO
The use of polysaccharides for thickening or gelling purposes is widely practised. When polysaccharides are dispersed in an aqueous medium, a hydrophilic colloid results which is particularly viscous in nature. Such viscous solutions, gels or pastes have found general use as thickeners in a wide range of applications, for example, paints, textiles, food products, printing inks, pharmaceuticals and explosives.
In many applications, the stability of polysaccharide-thickened aqueous solutions has been difficult to maintain overlong time periods, especially when the gels are exposed to above-a~bient temperatures. This loss of stability is evident i~ a breakdown of the gels, separation of the ingredients, or in syneresis. The prior art describes various methods for stabilizing the viscosity of these thickened solutions. These methods include, for example, the heating of the dry poly-saccharide prior to dissolution, treating the polysaccharide with various chemicals, such as, Pthylene glycol, SO2, or with various acids. In United States Patent No. 3,007,879, the inclusion in the solution of an iron inactivating agent is suggested, e.g., citric, oxalic and tartaric acids. In Canadian Patent ~o.
658,527, the addition of a water soluble thio-organic compound is ...
.,~,,.~ ~
o~
The use of polysaccharides for thickening or gelling purposes is widely practised. When polysaccharides are dispersed in an aqueous medium, a hydrophilic colloid results which is particularly viscous in nature. Such viscous solutions, gels or pastes have found general use as thickeners in a wide range of applications, for example, paints, textiles, food products, printing inks, pharmaceuticals and explosives.
In many applications, the stability of polysaccharide-thickened aqueous solutions has been difficult to maintain overlong time periods, especially when the gels are exposed to above-a~bient temperatures. This loss of stability is evident i~ a breakdown of the gels, separation of the ingredients, or in syneresis. The prior art describes various methods for stabilizing the viscosity of these thickened solutions. These methods include, for example, the heating of the dry poly-saccharide prior to dissolution, treating the polysaccharide with various chemicals, such as, Pthylene glycol, SO2, or with various acids. In United States Patent No. 3,007,879, the inclusion in the solution of an iron inactivating agent is suggested, e.g., citric, oxalic and tartaric acids. In Canadian Patent ~o.
658,527, the addition of a water soluble thio-organic compound is ...
.,~,,.~ ~
o~
- 2 - C-I-L 656 proposed. United States Patent No. 3,251,781 advocates the i~clusion of oxides and suIphides of selected metals in water solutions of galactomannan gums. In United States Patent Nos.
3,202,556, 3t301,723, 3,445,305 and 3r4851686l the use of various crosslinking or chelating agents is disclosed to stabilize galactomannan-water mixtures.
While all of the above-noted discoveries are meritorious, none is completely successful as a stabili2ation technique, particularly when the polysaccharide-thickened aqueous solution is exposed to above ambient temperatures for any length of time~
According to the present invention, the stability of polysaccharide-thickened aqueous solu~ions can be markedly improved by including in such solutions a water-insoluble, sulphur-containing compound in which a sulphur atom is bonded to a carbon atom, a nitrogen atom or to another sulphur atom.
Such compounds, for example, thiuram sulphides, thiomorpholines and the like, are exemplified by the structures below:
R \ S S / R2 1 / N - C (S)n - C - N \
R' R3 where n = 1 or 2 1 R2 R3 = CH3, C2H5~ C3H7, C~Hg or CH2 ~~ CH~ / 2 CH2 II O ~ - S - S - N
\C
Particularly preferred are the following commerically available compounds:
Tetrabutyl thiuram disulphide Tetraethyl thiuram disulphide Tetramethyl thiuram disulphide Dithiomorpholine Tetramethyl thiuram monosuIphide.
These stabilizers are in the form of a dry powder or an oily liquid (tetrabutyl thiuram disulphide).
Typical water soluble polysaccharide thickeners which may be stabilized by the method of the invention include, for example, gum arabic, agar-agar, Irish moss~ locust bean, tumerind, psyllium, xanthan or guar gums, starches and hydroxy-ethyl cellulose.
The polysaccharide-thickened aqueous solutions s~abilized by the method of the present invention will normally contain from 0.05~ to about 10% of polysaccharide-thickening agent, based on the total weight of ~ater and thickener. The stabilizer ,~ 20 comprises from 0.01% to about 1%, preferably, from 0.03% to 0.5% by weight of the total composition and will generally be in proportion to the amount of thickener present.
The thickened aqueous solution may be stabilized either by blending the stabilizer and polysaccharide thickener prior ~o addition to the water or the stabilizer may be added with vigorous stirring to an already thickened or to an unthickened aqueous medium. ~ecause of the substantially insoluble nature of the stabilizer, adequate mixiny is required to obtain optimum results.
The ~ollowing Examples will further describe the present invention.
A typical test aqueous salt solution was prepared similar to those employed in many slurry explosives or pharmaceutical formulations as ollows:
5~5
While all of the above-noted discoveries are meritorious, none is completely successful as a stabili2ation technique, particularly when the polysaccharide-thickened aqueous solution is exposed to above ambient temperatures for any length of time~
According to the present invention, the stability of polysaccharide-thickened aqueous solu~ions can be markedly improved by including in such solutions a water-insoluble, sulphur-containing compound in which a sulphur atom is bonded to a carbon atom, a nitrogen atom or to another sulphur atom.
Such compounds, for example, thiuram sulphides, thiomorpholines and the like, are exemplified by the structures below:
R \ S S / R2 1 / N - C (S)n - C - N \
R' R3 where n = 1 or 2 1 R2 R3 = CH3, C2H5~ C3H7, C~Hg or CH2 ~~ CH~ / 2 CH2 II O ~ - S - S - N
\C
Particularly preferred are the following commerically available compounds:
Tetrabutyl thiuram disulphide Tetraethyl thiuram disulphide Tetramethyl thiuram disulphide Dithiomorpholine Tetramethyl thiuram monosuIphide.
These stabilizers are in the form of a dry powder or an oily liquid (tetrabutyl thiuram disulphide).
Typical water soluble polysaccharide thickeners which may be stabilized by the method of the invention include, for example, gum arabic, agar-agar, Irish moss~ locust bean, tumerind, psyllium, xanthan or guar gums, starches and hydroxy-ethyl cellulose.
The polysaccharide-thickened aqueous solutions s~abilized by the method of the present invention will normally contain from 0.05~ to about 10% of polysaccharide-thickening agent, based on the total weight of ~ater and thickener. The stabilizer ,~ 20 comprises from 0.01% to about 1%, preferably, from 0.03% to 0.5% by weight of the total composition and will generally be in proportion to the amount of thickener present.
The thickened aqueous solution may be stabilized either by blending the stabilizer and polysaccharide thickener prior ~o addition to the water or the stabilizer may be added with vigorous stirring to an already thickened or to an unthickened aqueous medium. ~ecause of the substantially insoluble nature of the stabilizer, adequate mixiny is required to obtain optimum results.
The ~ollowing Examples will further describe the present invention.
A typical test aqueous salt solution was prepared similar to those employed in many slurry explosives or pharmaceutical formulations as ollows:
5~5
- 4 - C-I-L 656 S60 parts by wt. ammonium nitrate (tech. grade) 133.5 " " " sodium nitrate " "
1.5 " " " zinc nitrate "
205 " " " water (steam distil1`ate) ~
Seven measured proportions of the test solution in glass beakers were thickened by adding 0.67% by wt. of chemically unmodified guar gum (JaGUAR 170, Reg. T.M. Celanese Corp.3. To the separate thickened proportions of test solution was added 0.1%
by wt. of different stabilizers. The apparent viscosi~y of the thickened and stabilized solution was measured as made and after storage for 100 hours at 60C. Viscosity was measured using a Brookfield ~BT instrument with spindle No. 1 at rpm of 0.5, 1, 2.5 and 5. The results at 0.5 and 1.0 rpm were extrapolated to zero rmp to give a "zero shear" apparent viscosity. (The results at 2.5 and 5 rpm can be used to check the accuracy of the 0.5 rpm apparent viscosity). The results are shown in Table I below~
/
1.5 " " " zinc nitrate "
205 " " " water (steam distil1`ate) ~
Seven measured proportions of the test solution in glass beakers were thickened by adding 0.67% by wt. of chemically unmodified guar gum (JaGUAR 170, Reg. T.M. Celanese Corp.3. To the separate thickened proportions of test solution was added 0.1%
by wt. of different stabilizers. The apparent viscosi~y of the thickened and stabilized solution was measured as made and after storage for 100 hours at 60C. Viscosity was measured using a Brookfield ~BT instrument with spindle No. 1 at rpm of 0.5, 1, 2.5 and 5. The results at 0.5 and 1.0 rpm were extrapolated to zero rmp to give a "zero shear" apparent viscosity. (The results at 2.5 and 5 rpm can be used to check the accuracy of the 0.5 rpm apparent viscosity). The results are shown in Table I below~
/
5~Q3 TABLE I
StabiliZation of the Vi5c05ity-of an Un~odified tChemically) Guar JaGUAR-170 ~ ~Celanese Corp.) Guar Level 0.67% wt/wt VISCOSITY H~LF ~ELE L~
IEVEL . .INITIaL 100 HRS. IIFF. WITHOUr EX. STABILIZER WT/WT pH VISCOSITY _60C (HRS~ SIABILIZER(HRS~
1 Tetrabu~yl ~hiuram 0-1% 4-235,000 10,000 63 40 Disulphide ButylTU~DS
2 Tetraethyl Thiuram 0.1% 4.5 44,000 14,500 63 48 Disulphide EthylTUADS
3 Tetram~thyl miuram 0.1% 4.5 35,000 17,000 103 48 Dis~hide Methyl-TUAD ~ Tread Grade 4 Dithicm~rpholine 0.1% 4.3 13,000 4,900 72 40 : Sulfasan R ~
5 Tetramethyl miuram~ 0.1% 4.131,000 9,000 ~5 40 Disulphide Ihiurad~
StabiliZation of the Vi5c05ity-of an Un~odified tChemically) Guar JaGUAR-170 ~ ~Celanese Corp.) Guar Level 0.67% wt/wt VISCOSITY H~LF ~ELE L~
IEVEL . .INITIaL 100 HRS. IIFF. WITHOUr EX. STABILIZER WT/WT pH VISCOSITY _60C (HRS~ SIABILIZER(HRS~
1 Tetrabu~yl ~hiuram 0-1% 4-235,000 10,000 63 40 Disulphide ButylTU~DS
2 Tetraethyl Thiuram 0.1% 4.5 44,000 14,500 63 48 Disulphide EthylTUADS
3 Tetram~thyl miuram 0.1% 4.5 35,000 17,000 103 48 Dis~hide Methyl-TUAD ~ Tread Grade 4 Dithicm~rpholine 0.1% 4.3 13,000 4,900 72 40 : Sulfasan R ~
5 Tetramethyl miuram~ 0.1% 4.131,000 9,000 ~5 40 Disulphide Ihiurad~
6 Tetramethyl miuram 0.1% 4.2 30,500 9,800 60 40 Monosulphid~
Monothiurad ~
Monothiurad ~
7 None - 4.2 35,0007,000 - 40 pH as measured by Fisher Accumot (Reg. T.M~) pH meter Model 600 * Time taken for viscosity to drop to half its initial value.
As can be seen from Table I, the composition sample No. 7 devoid of stabilizer exhibited a substantially sharper drop in viscosity after storage than all other samples. Also, the viscosity half life (time for viscosity to drop to half its initial value) was substantially improved in presence of the stabilizer.
- ;
o~ ~
.
A series of salt-containing aqueous test solutions were prepared in glass beakers as in ~xamples 1-7. A portion of a known stabilizer was added to separate samples of the solution and the viscosity measured as made and after 100 hours storage at 60~C~ The results are tabulated in Table II below.
TABLE II
Known Stabilizers H~LF
VISCOS~ H~LF LIFE
L~ L~ INITIAL 10~ HRS L~ WITHOUT
EX. GUAR WT~T STABILIZER WT/WT VISCOSITY ~ 60C pH (HRS) S~AB~HRS)
As can be seen from Table I, the composition sample No. 7 devoid of stabilizer exhibited a substantially sharper drop in viscosity after storage than all other samples. Also, the viscosity half life (time for viscosity to drop to half its initial value) was substantially improved in presence of the stabilizer.
- ;
o~ ~
.
A series of salt-containing aqueous test solutions were prepared in glass beakers as in ~xamples 1-7. A portion of a known stabilizer was added to separate samples of the solution and the viscosity measured as made and after 100 hours storage at 60~C~ The results are tabulated in Table II below.
TABLE II
Known Stabilizers H~LF
VISCOS~ H~LF LIFE
L~ L~ INITIAL 10~ HRS L~ WITHOUT
EX. GUAR WT~T STABILIZER WT/WT VISCOSITY ~ 60C pH (HRS) S~AB~HRS)
8 J170* 0.67% miourea 0.1%32,000 7,400 4.1 48 40
9 J170 0.67% Sodium 0.1~ 46,00012,600 4.254 40 Thiosulphate J170 0.67% Ethylene 1.0% 12,0002,000 4.245 50 40 Glycol 11 J170 0.67% Sodium Sulphite(~) 0.1%26,000 7,200 4.4 54 44 20 12 J170 0.67% None - 35,0007,000 4.2 ~ 40 Adjustment of the pH was necessary.
* ~aGUAR 170 (Reg. T.M. Celanese Corp.) The results in Table II show that the use of known stabilizer was less eEficient in maintaining stability during 25 storage than were the stabilizers of the present invention.~
(Table I). Also, the viscosity half life was generally less using known stabilizers~
Various quantities of tetramethyl thiuram disulphide were added to separate guar-thickened samples of test solution (as per Examples 1-7) and the viscosity measured as made and aEter 50 hours storage at 60C. The results are tabulated in Table III
below.
TABLE III
Eff t of Tetramethyl Thiuram Disulphide_ Stability at pH 4.2 sing JaGUAR 170R as the Guar at 0.67~
STABILIZER INITIAL VISCCSITY H~LF ~F LI~THOUT
EX. L~ WT/WT VIS~OSITY 50 ~E~ @ 60C LIFE~RS) STABIIIZER ~HRS) 13 0.01% 36,500 17,000 ~6 40 14 0.05% 30,000 18,000 72 40 0.1~ 32,000 19,800 72 ~0 16 0.2~ 31,00016,100 53 ~0 17 0.3~ 32,60016,500 50 40 18 None 35,0007,000 - 40 As will be seen from Table III, the stabilizer is effective over a relatively wide range of concentration. The larger concentra-tions used (Examples 16 and 17) do not necessarily provide the greatest improvement in storage stability.
A number of different polysaccharide thickeners were added to samples of test solution (as per Examples 1-7) with and without various a~ded thiuram disulphide stabilizers. The viscosity was measured as made and after 100 hours storage at 60C. The results are shown in Table IV below.
TABLE IV
Compar_ on of various polysaccharide thickeners LEVEL LEVEL
XAMPLE THICKENER ` WT/WT `STABILIZER WT/WT
19 JaGUAR 170 ~ 0.67% - TMT ~ 0.1%
JaGUAR 170 0.67% Non~ - -21 JaGUAR HP-8 ~ 0.67% TMT 0.1%
(hydroxypropyl guar~
22 JaGUAR HP-8 0.67% Nona (hydroxypropyl guar) 23 NGL 8529 ~ 1.0% TBT ~ 0.1%
~oxidized guar) 24 NGL 8529 1.0% None . ~oxidized guar) GALACTSOL 423 ~ 1.5% TMT 0.1%
~oxidized guar) 26 GALACTSOL 423 1.5% None (oxidized guar) 27 Tapioca 2.0% TMT 0.1%
28 Tapioca 2.0% None 29 Psyllium gum 2.0% TMT 0.1%
Psyllium gum 2.0% None 31 Pregelatinized 5.0% TMT 0.1%
corn starch 32 Pregelatinized 5.0% None - corn starch 33 Xanthan gum 2.0% TMT 0.1 34 Xanthan gum 2.0% None cont~
- 9 - C~I-L 656 TABLE IV tcont.) Comparison of various polysaccharide thickeners IMTITIAL VISCQSITY 100 HALF LIFE HA1F LIFE WITH~T
EXAMPLE VISCOSITY HRS. ~ 6 0 C pH (HRS ) STABILIZER (HRS) 1935,000 17,000 4.5 103 44 2035,000 7,000 4~2 - 44 2117,000 10,700 4.5 lS0 45.5 2216,500 3,400 4.5 - 45.5 233,900 1,400 4.3 65 44 243,600 630 4.3 - ~4 2517,050 13,800 4.3 31~ 118 2613,600 7,400 4.3 - 118 2729,000 13~000 4.1 90 61 2829,500 9,400 4.1 _ 61 2929,200 22,000 5.~ 274 96 3019,600 8,500 5.5 - 96 318,~00 ~1,000 ~ 4.1 3212,500 ~ 290 ~ 4.1 - -33605,000310,000 ~ 4.199.6 days 88.5 days 34710,000405,000 ~ 4.1 - 88.5 days Tetramethyl thiuram disulphide MethylTUAD~ Thread Grade Tetrabutyl thiuram disulphide At 19 days Q At 70 days Viscosity measured using a Brookfield RVT inst:rument with a #l Brookfield spindle at 60C extrapolated to zero shear.
* ~aGUAR 170 (Reg. T.M. Celanese Corp.) The results in Table II show that the use of known stabilizer was less eEficient in maintaining stability during 25 storage than were the stabilizers of the present invention.~
(Table I). Also, the viscosity half life was generally less using known stabilizers~
Various quantities of tetramethyl thiuram disulphide were added to separate guar-thickened samples of test solution (as per Examples 1-7) and the viscosity measured as made and aEter 50 hours storage at 60C. The results are tabulated in Table III
below.
TABLE III
Eff t of Tetramethyl Thiuram Disulphide_ Stability at pH 4.2 sing JaGUAR 170R as the Guar at 0.67~
STABILIZER INITIAL VISCCSITY H~LF ~F LI~THOUT
EX. L~ WT/WT VIS~OSITY 50 ~E~ @ 60C LIFE~RS) STABIIIZER ~HRS) 13 0.01% 36,500 17,000 ~6 40 14 0.05% 30,000 18,000 72 40 0.1~ 32,000 19,800 72 ~0 16 0.2~ 31,00016,100 53 ~0 17 0.3~ 32,60016,500 50 40 18 None 35,0007,000 - 40 As will be seen from Table III, the stabilizer is effective over a relatively wide range of concentration. The larger concentra-tions used (Examples 16 and 17) do not necessarily provide the greatest improvement in storage stability.
A number of different polysaccharide thickeners were added to samples of test solution (as per Examples 1-7) with and without various a~ded thiuram disulphide stabilizers. The viscosity was measured as made and after 100 hours storage at 60C. The results are shown in Table IV below.
TABLE IV
Compar_ on of various polysaccharide thickeners LEVEL LEVEL
XAMPLE THICKENER ` WT/WT `STABILIZER WT/WT
19 JaGUAR 170 ~ 0.67% - TMT ~ 0.1%
JaGUAR 170 0.67% Non~ - -21 JaGUAR HP-8 ~ 0.67% TMT 0.1%
(hydroxypropyl guar~
22 JaGUAR HP-8 0.67% Nona (hydroxypropyl guar) 23 NGL 8529 ~ 1.0% TBT ~ 0.1%
~oxidized guar) 24 NGL 8529 1.0% None . ~oxidized guar) GALACTSOL 423 ~ 1.5% TMT 0.1%
~oxidized guar) 26 GALACTSOL 423 1.5% None (oxidized guar) 27 Tapioca 2.0% TMT 0.1%
28 Tapioca 2.0% None 29 Psyllium gum 2.0% TMT 0.1%
Psyllium gum 2.0% None 31 Pregelatinized 5.0% TMT 0.1%
corn starch 32 Pregelatinized 5.0% None - corn starch 33 Xanthan gum 2.0% TMT 0.1 34 Xanthan gum 2.0% None cont~
- 9 - C~I-L 656 TABLE IV tcont.) Comparison of various polysaccharide thickeners IMTITIAL VISCQSITY 100 HALF LIFE HA1F LIFE WITH~T
EXAMPLE VISCOSITY HRS. ~ 6 0 C pH (HRS ) STABILIZER (HRS) 1935,000 17,000 4.5 103 44 2035,000 7,000 4~2 - 44 2117,000 10,700 4.5 lS0 45.5 2216,500 3,400 4.5 - 45.5 233,900 1,400 4.3 65 44 243,600 630 4.3 - ~4 2517,050 13,800 4.3 31~ 118 2613,600 7,400 4.3 - 118 2729,000 13~000 4.1 90 61 2829,500 9,400 4.1 _ 61 2929,200 22,000 5.~ 274 96 3019,600 8,500 5.5 - 96 318,~00 ~1,000 ~ 4.1 3212,500 ~ 290 ~ 4.1 - -33605,000310,000 ~ 4.199.6 days 88.5 days 34710,000405,000 ~ 4.1 - 88.5 days Tetramethyl thiuram disulphide MethylTUAD~ Thread Grade Tetrabutyl thiuram disulphide At 19 days Q At 70 days Viscosity measured using a Brookfield RVT inst:rument with a #l Brookfield spindle at 60C extrapolated to zero shear.
- 10 - C-I-L 656 The results in Table IV demonstrate that the stabilizers of the invention may be employed with a wide range of water-soluble polysaccharide thickeners~
Claims (7)
1. A method of stabilizing a polysaccharide-thickened aqueous medium which comprises adding to a polysaccharide/water mixture from .01% to 1% by weight of the total composition of a water-insoluble, oxidizable, sulphur-containing compound in which a sulphur atom is bonded to a carbon atom, a nitrogen atom or to another sulphur atom.
2. A method as claimed in Claim 1 wherein the sulphur-containing compound is selected from the group of tetrabutyl thiuram disulphide, tetraethyl thiuram disulphide, tetramethyl thiuram disulphide, dithiomorpholine and tetramethyl thiuram monosulphide.
3. A method as claimed in Claim 1 wherein the polysaccharide-thickened aqueous medium is an aqueous salt solution.
4. A method as claimed in Claim 1 wherein the polysaccharide thickener is selected from the group of modified and unmodified guar, tapioca, psyllium,xanthan and corn starch.
5. A stable aqueous gel comprising a mixture of water and a polysaccharide thickener and from .01% to 1% by weight of the total composition of stabilizer comprising a water-insoluble, oxidizable, sulphur-containing compound in which a sulphur atom is bonded to a carbon atom, a nitrogen atom or to another sulphur atom.
6. An aqueous gel as claimed in Claim 5 wherein the sulphur-containing compound is selected from the group of tetra-butyl thiuram disulphide, tetraethyl thiuram disulphide, tetra-methyl thiuram disulphide, dithiomorpholine and tetramethyl thiuram monosulphide.
7. An aqueous gel as claimed in Claim 5 wherein the polysaccharide thickener is selected from the group of modified and unmodified guar, tapioca, psyllium, xanthan and corn starch.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000425914A CA1185405A (en) | 1983-04-14 | 1983-04-14 | Stabilized, polysaccharide-thickened aqueous solutions |
| ZA838910A ZA838910B (en) | 1983-04-14 | 1983-11-30 | Stabilized,polysaccharide-thickened aqueous solutions |
| ZW263/83A ZW26383A1 (en) | 1983-04-14 | 1983-12-05 | Stabilized,polysaccharide-thickened aqueous solutions |
| US06/580,188 US4514318A (en) | 1983-04-14 | 1984-02-15 | Stabilizing polysaccharide-thickened aqueous medium and stable aqueous gel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000425914A CA1185405A (en) | 1983-04-14 | 1983-04-14 | Stabilized, polysaccharide-thickened aqueous solutions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1185405A true CA1185405A (en) | 1985-04-16 |
Family
ID=4125017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000425914A Expired CA1185405A (en) | 1983-04-14 | 1983-04-14 | Stabilized, polysaccharide-thickened aqueous solutions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4514318A (en) |
| CA (1) | CA1185405A (en) |
| ZA (1) | ZA838910B (en) |
| ZW (1) | ZW26383A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661266A (en) * | 1984-07-16 | 1987-04-28 | Nitto Chemical Industry Co., Ltd. | Completion and workover fluids |
| JPS61163986A (en) * | 1985-01-16 | 1986-07-24 | Nitto Chem Ind Co Ltd | Method for stabilizing fracturing fluid |
| JPS61275374A (en) * | 1985-05-31 | 1986-12-05 | Nitto Chem Ind Co Ltd | Method of stabilizing fracturing fluid |
| US4774093A (en) * | 1985-06-25 | 1988-09-27 | Fmc Corporation | Polysaccharide compositions, preparation and uses |
| GB8828795D0 (en) * | 1988-12-09 | 1989-01-18 | Univ Nottingham | Improvements in/relating to polysaccharide systems |
| US5462688A (en) * | 1993-08-20 | 1995-10-31 | Gojo Industries, Inc. | Flowable, pumpable cleaning compositions and method for the preparation thereof |
| US5523014A (en) * | 1994-05-16 | 1996-06-04 | Gojo Industries, Inc. | Flowable, pumpable cleaning compositions and method for the preparation thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2870059A (en) * | 1956-08-15 | 1959-01-20 | Du Pont | Process of molding dithiocarbamate slurries which contain guar gum |
| US3084057A (en) * | 1960-01-27 | 1963-04-02 | Gen Mills Inc | Gum sols of improved heat stability |
| US3146200A (en) * | 1960-08-11 | 1964-08-25 | Stein Hall & Co Inc | Stabilized galactomannan gum solutions and process |
| US3251781A (en) * | 1961-08-21 | 1966-05-17 | Gen Mills Inc | Organo-metallic gel-producing compositions and processes for preparing organo-metallic gels |
-
1983
- 1983-04-14 CA CA000425914A patent/CA1185405A/en not_active Expired
- 1983-11-30 ZA ZA838910A patent/ZA838910B/en unknown
- 1983-12-05 ZW ZW263/83A patent/ZW26383A1/en unknown
-
1984
- 1984-02-15 US US06/580,188 patent/US4514318A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US4514318A (en) | 1985-04-30 |
| ZA838910B (en) | 1984-08-29 |
| ZW26383A1 (en) | 1985-07-03 |
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