Dialkylaminoalkyl-hydroxyalkyl ethers of polygalactomannans

Abstract: Dialkylaminoalkyl-hydroxyalkyl ethers of polygalactomannan are useful as thickening agents for aqueous fluids. The viscosity of the thickened fluids may be reduced by addition of an alkali metal hypochlorite, an alkaline earth metal hypochlorite or a chlorinated isocyanurate.

Description: The Field of the Invention This invention pertains to water-soluble polymers, in particular to certain derivatives of polygalactomannans. In one aspect, this invention pertains to a double derivative of a polygalactomannan. In another aspect, this invention relates to thickened aqueous fluids made from the double derivative. In still another aspect, this invention pertains to a process for reducing the viscosity of thickened aqueous fluids. Background of the Invention Polygalactomannans, particularly the naturally occurring guar gum and locust bean gum, have been known for some time and have found many industrial uses. To improve the performance of these gums and to widen their fields of use, polygalactomannans have been modified by reaction with various reagents to form derivatives of the gums. Examples of such derivatives are hydroxyalkyl ethers of polygalactomannans, aminoalkyl ethers of polygalactomannans, mixed derivatives which are carboxyalkyl-hydroxyalkyl ethers and carboxyalkyl-aminoalkyl ethers of polygalactomannans. Hydroxyalkyl ethers of polygalactomannans are described in US Patent No. 3,326,890. Aminoalkyl ethers of the gums are disclosed in US Patent No. 3,498,912. Carboxyalkyl-hydroxyalkyl mixed derivatives are described in US Patent No. 3,723,409. Mixed derivatives containing both anionic groups, e.g., carboxyalkyl, and cationic groups, e.g., aminoalkyl, are disclosed in US Patent No. 3,467,647. An important use for polygalactomannans and their derivatives is as thickeners for industrial applications. However, after the purpose for using the thickened aqueous fluid has been served, it is often desirable to lower the viscosity of the fluid. This lowering of viscosity is accomplished by using a "breaker" which acts on the water-soluble polymer to reduce its molecular weight and to thin the fluid in which it is dissolved. The breaking of aqueous gels or thickened aqueous fluids has been accomplished by various techniques. One such method is to use the degradative action of acids, enzymes, or mild oxidizing agents as disclosed in US Patent No. 4,169,791. In US Patent No. 4,464,268, sodium hypochlorite is described as being a drastic treating agent for degrading water-soluble polymers. The use of ammonium and alkali metal persulfates in combination with tertiary amines is disclosed in US Patent No. 4,250,044 as being a suitable breaker system for high viscosity fluids. Lithium hypochlorite is described as a breaker material in Oil and Gas Journal , December 12, 1983, pp. 96-101. The thickening of aqueous fluids and various techniques for reducing the viscosity of the fluids are described in such patents as US Patents Nos. 3,002,960; 3,779,914; 4,144,179; and 4,552,668. As described in US Patent No. 4,654,043, starch sizing agents are degraded by treatment with hypochlorites and amino compounds. In US Patent No. 4,647,385, the viscosity of thickened aqueous solutions is reduced by the addition of alkali metal and alkaline earth metal salts of hypochlorous acid plus tertiary amines. The combination of the salt and the tertiary amine is much more efficient in speed of reduction in viscosity and in the completeness of the degradation of the polymer than the use of the metal salt alone. Thickened aqueous fluids are useful in oil recovery processes, particularly in the practice of fracturing subterranean formations. In the fracturing operations, a thickened fluid having granular insoluble particulate material suspended therein, is injected down a well penetrating the formation under hydraulic pressure. The pressurized fluid causes the formation to crack or fracture. The suspended insoluble granular particles are forced into the fractures and prop open the fractures when the fracturing pressures are released. Before the well is put back into operation, the thickened fluid must be removed from the well. Such removal is facilitated if the viscosity can be quickly reduced. Industry is constantly searching for improved and efficient thickeners for aqueous fluids and for more efficient breaker systems. DE-A-1,543,008 (corresponding to GB-A-1072021 and US-A-3,357,971) discloses an hydroxypropyl cellulose derivative containing an ionic substituent and having an hydroxypropyl M.S. of at least 2 and an ionic D.S. of 0.001 to 0.4. Suitable ionic substituents include ether substituents such as a carboxyalkyl ether, dialkylaminoalkyl or sulfoalkyl substituent, or an ester substituent, such as a sulfate substituent. Summary of the Invention The present invention provides ether derivatives of polygalactomannans containing both dialkylaminoalkyl ether and hydroxyalkyl groups. In such a compound (also referred to herein as a "composition (or polymer) of this invention"), the degree of substitution (DS) of the product, i.e., the amount of dialkylaminoalkyl ether substitution, in general ranges from 0.001 to 0.2. The molecular substitution (MS) of the product, i.e., the amount of hydroxyalkyl ether substitution, in general ranges from 0.05 to 1.6. The composition of this invention is used to thicken and to gel aqueous fluids for various applications. Such applications include the fracturing of subterranean formations penetrated by a borehole, use in oil and gas well drilling, completion and workover fluids and in industrial, personal care, carpet and textile dyeing, and waste treatment processes. When desired, the viscosity of the thickened or gelled fluids is reduced by the addition of a breaker material selected from alkali metal salts of hypochlorous acid, alkaline earth metal salts of hypochlorous acid and chlorinated isocyanurates. In applying this invention to the fracturing of subterranean formations penetrated by a borehole, a water-based fluid is injected into the borehole and into contact with the formation at a rate and pressure sufficient to fracture said formation wherein the water-based fluid is made from (a) an aqueous liquid, (b) as a thickening agent to increase the viscosity of the aqueous liquid, a viscosity-increasing amount of the polygalactomannan derivative, with insoluble granular material being preferably suspended in the thickened liquid, and (c) to reduce the viscosity of the fluid after the fluid has contacted the formation and after its intended purpose as a viscous fluid has been served, an effective amount of the breaker material. In the various applications of this invention, each of the tertiaryaminoalkyl ether-hydroxyalkyl ether derivative of the polygalactomannan and the breaker material may, of course, be constituted by a mixture of two or more compounds of the appropriate description. Description of Preferred Embodiments The water-soluble polymers of this invention are dialkylaminoalkyl-hydroxyalkyl ethers of polygalactomannans. These polymers may be made by reacting a polygalactomannan with a dialkylaminoalkyl halide or epoxide, and an alkylene oxide. The polygalactomannans from which the dialkyl aminoalkyl polygalactomannans are derived are hydrocolloid polysaccharides composed principally of galactose and mannose units and are usually found in the endosperm of leguminous seeds, such as guar, locust bean, honey locust, flame tree, and the like. Guar, for example, is composed mostly of a galactomannan which is essentially a straight chain mannan with single-membered galactose branches. The mannose units are linked in a 1,4-β-glycosidic linkage and the galactose branching takes place by means of a 1-6 linkage on alternate mannose units. The ratio of galactose to mannose units in the guar polymer is one to two. Locust bean gum is also a polygalactomannan of similar molecular structure in which the ratio of galactose to mannose is one to four. Guar and locust bean gum are the preferred sources of the polygalactomannans, principally because of their commercial availability. The dialkyl aminoalkyl derivatizing agents useful in this invention include dialkylaminoalkyl halides or epoxides wherein each alkyl group contains from 1 to 6 carbon atoms and wherein the total number of carbon atoms does not exceed 12. The halide is generally chloride, bromide or iodide, with the chloride being preferred. Examples of useful dialkylamino alkyl derivatizing agents are dimethylaminomethyl chloride, dimethylaminoethyl chloride, dimethylaminopropyl chloride, methylethylaminopropyl bromide, dimethylaminoisopropyl chloride, methylethylaminoisopropyl chloride, diethylaminobutyl iodide, 3-dimethylamino -1,2-epoxypropane, 3-diethylamino -1,2-epoxypropane, and other isomers. The hydroxyalkyl derivatizing agents useful in this invention include alkylene oxides, wherein the alkylene group contains from two to four carbon atoms and the epoxide group is on adjacent carbon atoms. Examples of alkylene oxides are ethylene oxide, propylene oxide-1,2, butylene oxide-1,2, and butylene oxide-2,3. The preferred alkylene oxide is propylene oxide-1,2. The compositions of this invention may be prepared by first forming the hydroxyalkyl ether derivative followed by the reaction with the dialkylaminoalkyl derivatizing agent. The polygalactomannan can be reacted with the derivatizing agents in powder or granular form, or in the form of splits. The reactions can be conducted in aqueous, non-aqueous, or mixed systems using alkali as the condensing or catalytic agent. When using powder or granular polygalactomannans, preferred reaction media are a lower alcohol-water mixture, e.g., methanol or isopropanol, and water. The preferred medium for reacting splits is water. The amount of alkali catalyst used in this reaction will in general vary from 0.1 to 5 weight percent based on the weight of the polygalactomannan. When the dialkylaminoalkyl derivatizing agent is a halide or halide salt, then the amount of alkali used is at least equivalent to the halide in the derivatizing agent, and, preferably, is in excess of the halide. The reaction of alkylene oxides with polygalactomannans is described in detail in US Patents Nos. 3,326,890 and 3,723,409. The reaction of polygalactomannans with dialkylaminoalkyl halides or epoxides is described in US Patent No. 3,498,912. The compositions of this invention have a hydroxyalkyl ether substitution of in general from 0.05 to 1.6 moles per galactomannan unit (MS) and, preferably, 0.3 to 1.0. The tertiaryaminoalkyl ether substitution will in general vary from 0.001 to 0.2 mole per galactomannan unit (DS) and, preferably, from 0.004 to 0.1. The reduction in viscosity of aqueous solutions of the compositions of this invention is conducted by adding to the solutions an alkali metal or alkaline earth metal salt of hypochlorous acid, or a chlorinated isocyanurate. The hypochlorite salts include magnesium hypochlorite, calcium hypochlorite, strontium hypochlorite, lithium hypochlorite, sodium hypochlorite, and potassium hypochlorite. The preferred salts are sodium and calcium hypochlorite. The chlorinated isocyanurates useful in this invention include trichloro-s-triazine trione, sodium dichloro-s-triazine trione, potassium dichloro-s-triazine trione, sodium dichloro-s-triazine trione dihydrate, and mixtures thereof. The reduction in viscosity of aqueous fluids made according to this invention, is conducted on aqueous fluids which are thickened with in general from 10 to 80 pounds of dialkylaminoalkyl hydroxyalkyl polygalactomannan per 1000 gallons of aqueous fluid (1.2 to 9.6 kg per 1000 litres). Preferably the amount of dialkylaminoalkyl hydroxyalkyl polygalactomannan will be from 20 to 60 pounds per 1000 gallons (2.4 to 7.2 kg per 1000 litres). The amount of metal hypochlorite or chlorinated isocyanurate used to reduce the viscosity of the thickened aqueous fluid will vary in general from 0.1 to 5 pounds per 1000 gallons of aqueous fluid (0.012 to 0.6 kg per 1000 litres) and preferably from 0.5 to 2 pounds per 1000 gallons (0.06 to 0.24 kg per 1000 litres). The thickened aqueous fluid prior to the addition of the hypochlorite salt or chlorinated isocyanurate usually has a pH of from 6 to 11 and, preferably, 7 to 10. The temperature of the system will usually be from 50°F to 300°F (10° to 149°C). The breaker systems of this invention are particularly useful at temperatures of 70° to 250°F (21° to 121°C). The following examples illustrate the invention in more detail. Parts and percentages are by weight unless otherwise designated. Example 1 To a suitable reactor were added 69.3 parts of powdered hydroxypropyl guar having an MS of 0.4 and 125 parts of isopropyl alcohol. Agitation was begun and a nitrogen sparge was applied. With the temperature at 18°C, a solution of 11.9 parts of dimethylaminopropyl chloride hydrochloride in 35 parts of deionized water was added over a period of 20 minutes. After 10 minutes, the addition of a solution of 8 parts of sodium hydroxide in 35 parts of water was begun and completed in 20 minutes with the temperature rising to 23°C. Heat was applied raising the temperature to 70°C in 35 minutes. The temperature was held at 70°C for 1 hour and was then lowered to 21°C. The reactor contents were mixed with 500 parts by volume of a 60/40 methanol/water solution. After soaking for 30 minutes, the liquid phase was removed and discarded. Another 500 parts of methanol and water (60/40) were added and after soaking for 30 minutes, the liquid phase was removed and discarded. The swollen gum product was mixed with 1000 parts of acetone and was allowed to soak for 30 minutes. The mixture was vacuum filtered on a Buchner funnel and was washed with 300 parts of acetone. The gum product was spread on a tray and dried overnight. Seventy-one parts of air dried product were recovered. A solution of the guar product in deionized water was prepared in the proportions of 40 pounds of the guar derivative to 1000 gallons of solution (40 lbs/1000 gal = 4.79 kg/1000 litres). After hydrating for 2 hours at pH 6.0, the pH was adjusted to 8.0 with dilute aqueous sodium hydroxide. The viscosity of the solution was 127 Fann Units. A 3% aqueous calcium hypochlorite solution, 0.9 ml, was added to 400 ml of the thickened solution. The viscosity dropped to 22 Fann units in one minute. Example 2 To a suitable reactor were added 90 parts of powdered hydroxypropyl guar, (M.S 0.4), and 175 parts of isopropyl alcohol. Nitrogen sparging and agitation were begun. After 15 minutes with the temperature at 21°C, a solution of 0.1 part of the methyl ether of hydroquinone, 0.1 part of citric acid and 25 parts of deionized water was added over a five-minute period. After 10 minutes, a solution of 7.9 parts of dimethylaminopropyl chloride hydrochloride in 25 parts of water was added over 15 minutes. After 10 minutes, a solution of 6 parts of sodium hydroxide in 40 parts of water was added over 12 minutes. The temperature was then raised to 75°C over 33 minutes and was held at 75°C for 2 hours and 30 minutes. The temperature was then lowered to 22°C. The reactor contents were washed three times with 1000 parts by volume of a 60/40 mixture of methanol and water. After each washing, the liquid phase was removed by decantation. The gum product was then mixed with 500 parts by volume of methanol. The liquid phase was separated from the gum product by vacuum filtration on a Buchner funnel. The funnel contents were then washed with 500 parts of acetone again using vacuum. The product was spread on a tray and was dried over the weekend at room temperature. 82.2 parts of guar product were recovered. Example 3 To a suitable reactor were added 90 parts of powdered guar and 200 parts of isopropyl alcohol. Agitation and nitrogen sparge were begun. After 1 hour and 5 minutes, a solution of 6 parts of sodium hydroxide in 50 parts of water was added over 20 minutes. After holding for 10 minutes and with the temperature at 24°C, the addition of 29 parts of propylene oxide was begun and completed in 5 minutes. The temperature was raised to 60°C in 20 minutes and was held at 60°C for 2 hours and 5 minutes. A solution of 7.9 parts of dimethylaminopropyl chloride hydrochloride was then added over 30 minutes. The temperature was raised to 70°C in 15 minutes and was held at 70°C for two hours. The temperature was then lowered to room temperature. After washing, dehydrating, and drying using the procedure of Example 2, 91.4 parts of product were recovered. Example 4 To a suitable reactor were added 1760 parts of deionized water, 170 parts of 50% sodium hydroxide in water, and 4 parts of borax. The temperature was raised to 170°F (76.7°C) and 2000 parts of double purified guar splits were added. The reactor was sealed and was purged three times with nitrogen. Vacuum to -10 inches of mercury (-33.9 kPa) was applied and 450 parts of propylene oxide were added with the temperature at 144°F (62.2°C). The temperature was raised 162°F (72.2°C) and the pressure was held at 10 psig (68.9 kPa) by controlling the propylene oxide addition. The addition of propylene oxide was completed in 56 minutes. The temperature was held at 159-162°F (70.6-72.2°C) until the pressure dropped to -5 inches of mercury (-16.9 kPa). The reactor was then purged twice with nitrogen and was pressured with nitrogen to 5 psig (34.5 kPa). After holding for 5 minutes at 159°F (70.6 °C), purging with nitrogen and pressurizing were repeated. The pressure was lowered to -10 inches of mercury (-33.9 kPa) and a solution of 176 parts of dimethylaminopropyl chloride hydrochloride in 740 parts of water was added. The temperature was held at 160°F (71.1°C) for 10 minutes. A 50% solution of sodium hydroxide (350 parts) and 100 parts of water were added. Heating at 160°F (71.1°C) was continued for 2 hours. The reactor contents were cooled to room temperature and were washed 3 times with water. The derivatized guar splits were then milled and dried under heated air (550°F/287.8°C). Example 5 Thickened solutions were prepared from the derivatized guar products of Examples 1, 2, 3 and 4 by adding the guar to water containing 2 percent potassium chloride in the proportions of 40 pounds of derivatized guar to 1000 gallons of solution (4.79 kg/1000 litres). After hydrating for two hours, the pH was adjusted to 8.0 with dilute sodium hydroxide. The viscosity was determined with a Fann Model 35 Viscometer. A 3% aqueous solution of calcium hypochlorite was added in the proportion of 2.25 gallons per 1000 gallons (2.25 litres per 1000 litres). The viscosity was then determined at intervals over 10 minutes. The viscosity determinations are listed in the table. Example Viscosity (cps or mPas) Init 30 sec. 1 min. 2 min. 5 min. 10 min. 1 25 6 4 4 4 4 2 36 10 9 8 8 8 3 33 9 7 5 4 4 4 38 11 10 10 10 10

Claims: A polygalactomannan ether containing both dialkylaminoalkyl ether and hydroxyalkyl ether groups. A compound according to claim 1, characterised in that the degree of substitution (DS) of the dialkylaminoalkyl ether group is from 0.001 to 0.2, and wherein the molecular substitution (MS) of the hydroxyalkyl ether group is from 0.05 to 1.6. A compound according to claim 2, characterised in that the DS is 0.004 to 0.1 and the MS is 0.3 to 1.0. A compound according to claim 1, 2 or 3, characterised in that the polygalactomannan is guar gum. A compound according to claim 1, 2 or 3, characterised in that the polygalactomannan is locust bean gum. A compound according to any of claims 1 to 5, characterised in that the alkyl groups in the dialkylaminoalkyl ether each contain from 1 to 6 carbon atoms and wherein the total number of carbon atoms in the alkyl groups does not exceed 12. A compound according to claim 6, characterised in that the dialkylaminoalkyl ether group is dimethylaminopropyl ether. A compound according to any of claims 1 to 7, characterised in that the alkyl group of the hydroxyalkyl ether contains 2 to 4 carbon atoms. A compound according to claim 8, characterised in that the hydroxyalkyl group is hydroxypropyl. An aqueous fluid that has been thickened with a dialkylaminoalkyl ether-hydroxyalkyl ether of a polygalactomannan according to any of claims 1 to 9. An aqueous fluid according to claim 10, characterised in that it contains 10 to 80 pounds of dialkylaminoalkyl ether, hydroxyalkyl ether of polygalactomannan per 1000 gallons of aqueous fluid (1.2 to 9.6 kg per 1000 litres). An aqueous fluid according to claim 11, characterised in that it contains 20 to 60 pounds of dialkylaminoalkyl ether-hydroxyalkyl ether of the polygalactomannan per 1000 gallons of aqueous fluid (2.4 to 7.2 kg per 1000 litres). An aqueous fluid according to claim 10, 11 or 12, characterised in that it is gelled. A process for reducing the viscosity of an aqueous fluid according to any of claims 10 to 13, characterised in that it comprises adding to the aqueous fluid a breaker material selected from alkali metal salts of hypochlorous acid, alkaline earth metal salts of hypochlorous acid and chlorinated isocyanurates. A process according to claim 14, characterised in that the breaker material is sodium hypochlorite, calcium hypochlorite or sodium dichloro-s-triazine trione. A process according to claim 14 or 15, characterised in that the breaker material is added in the amount of 0.1 to 5 pounds per 1000 gallons of aqueous fluid (0.012 to 0.6 kg per 1000 litres). A process according to claim 16, characterised in that the breaker material is added in the amount of 0.5 to 2 pounds per 1000 gallons of aqueous fluid (0.06 to 0.24 kg per 1000 litres).

Inventors: KARCHER DENNIS J, MORGAN MICHAEL E, PHELPS MARTHA A, KARCHER, DENNIS J., MORGAN, MICHAEL E., PHELPS, MARTHA A.
Applicants: STEIN HALL & CO INC, STEIN, HALL & CO., INC.
Application year: 1989
Main classification: C08B37
IPC codes: C09K8, C08B37, C09K3