SACCHARIDE POLYMERS WITH AMINE FUNCTIONALITY PREPARED BY OXIDATION WITH HYPOCHLORITE

Abstract

The present invention relates to a method characterized in that it comprises the steps of: exposing a saccharide polymer comprising one or more monosaccharide units linked by glycosidic bonds and comprising a trans-vicinal diol to an oxidizing reagent comprising sodium hypochlorite pentahydrate; reacting the trans-vicinal diol with the oxidizing reagent to form an oxidative opening site bearing at least one aldehyde; exposing the at least one aldehyde to an amine to form an imine intermediate at the oxidative opening site; and reducing the imine intermediate to a secondary or tertiary amine at the oxidative opening site to form a saccharide polymer with amine functionality.

Description

SACCHARIDE POLYMERS WITH AMINE FUNCTIONALITY PREPARED BY OXIDATION WITH HYPOCHLORITE CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority, pursuant to 35 USC § 119, from U.S. provisional patent application 62 / 875,122, filed on July 17, 2019, and incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION In many cases, recovering hydrocarbon resources, such as oil and gas, from underground formations containing water-sensitive minerals, such as clays, can be problematic. The crystalline structure of stratified silicate clays can become mechanically unstable in the presence of water and swell hydraulically, sometimes forming a thick, viscous fluid slurry. This can impair fluid flow within an underground formation and / or a wellbore penetrating the formation. Alternatively, the mechanical breakdown of clays can produce fine particles that gradually migrate from the bottom of the underground formation and the wellbore. Both types of degradation are problematic due to their potential to adversely affect fluid flow performance and / or promote formation damage, thereby leading to decreased fluid permeability.Complete occlusion of fluid flow paths or collapse of wellbore walls can occur in some cases of excessive clay swelling or destabilization. Clay stabilizers are substances that can be used to limit the effect of aqueous fluids on water-sensitive clays. As used herein, the term “clay stabilizer” refers to any substance that helps stabilize a clay mineral against interaction with an aqueous fluid, thereby decreasing or eliminating the clay mineral’s propensity to swell and / or migrate in the form of fine particles. Clay stabilizers are typically placed in a carrier fluid, generally an aqueous carrier fluid, for interaction with a clay mineral. In many cases, clay stabilizer fluids contain inorganic salts, such as potassium chloride, which can interact with a clay surface and promote ion exchange and dehydration of the clay structure with the fluid in order to increase clay stability.Potassium-loaded clays are much less prone to swelling and fine particle migration compared to the native (pre-exchanged) sodium form. Consolidating agents that physically bind clay particles together can also be suitable clay stabilizers in some cases. Suitable consolidating agents may include polymers, resins, and the like. High-molecular-weight polyacrylamide polymers can be used for this purpose. Polysaccharides with frzonnn / zznz / E / Yi amine functionality have also been used for clay stabilization in some cases, as described in U.S. Patent Application Publication 2016 / 0289559. Despite the rapid ability of inorganic salts and polymeric consolidating agents to moderate the instability of clay minerals, these substances do not represent a completely satisfactory and universal approach to the problem of clay stabilization in the presence of aqueous fluids. Fluids containing high concentrations of inorganic salts can be ecologically irresponsible for the wildlife and flora surrounding a drilling site, and the disposal of these fluids can be problematic. Furthermore, high salt concentrations can affect the proper functioning of fluids commonly introduced into a well, such as fracturing fluids and other gelled fluids. That is, high salt concentrations can lead to improper gelation or excessive fluid weight, which can result in improper fluid performance and / or placement.Polymeric consolidation agents can be costly in some cases, excessively increase fluid viscosity, adversely affect one or more other functional components of a treatment activity (for example, by rendering other functional components inactive or reducing their activity), and some may present their own toxicity issues. Biologically derived polymers can alleviate some of these problems, but access to particular polymer structures of interest may be limited by the specific molecular structure of the biological source material. DETAILED DESCRIPTION OF THE INVENTION This disclosure relates generally to functional saccharide polymers and, more specifically, to functional saccharide polymers prepared from the selective oxidative opening of trans-vicinal diols in polysaccharides and oligosaccharides. Functional saccharide polymers can be effective in promoting clay control in several non-limiting ways. As discussed above, the interaction of clays with aqueous fluids can be problematic in many cases. Clay swelling and / or fine particle migration can occur when water-sensitive clays interact with aqueous fluids, which can lead to several undesirable subsurface outcomes, such as decreased formation permeability and / or surface abrasion within a wellbore. Although clay stabilizers can be used to mitigate detrimental interactions between aqueous fluids and water-sensitive clays, currently used clay stabilizers do not provide a completely satisfactory approach to the clay stabilization problem. That is, conventional clay stabilizers can present environmental problems, particularly inorganic salts, and some can be more expensive than desired.In some cases, biologically derived materials may not offer a range of frzonnn / zznz / E / Yi structural diversity desired. Functional saccharide polymers, such as dextran polymers with amine functionality and other polysaccharides with amine functionality, can be effective in promoting clay stabilization, as described in U.S. Patent Application Publication 2016 / 0289559, which is incorporated herein by reference in its entirety. Oligosaccharides with amine functionality, such as maltodextrin with amine functionality, can also be effective in promoting clay stabilization, as described in U.S. Patent Application Publication 2020 / 0017755, which is also incorporated herein by reference in its entirety.Saccharide polymers with amine functionality provide a considerably different approach to clay stabilization and are far more environmentally responsible than conventional clay stabilizers such as inorganic salts and fully synthetic polymers. The functional saccharide polymers described in U.S. Patent Application Publication 2016 / 0289559 and U.S. Patent Application Publication 2020 / 0017755 comprise multiple monosaccharide units (monomers) linked by glycosidic bonds. In the case of the polysaccharides described in U.S. Patent Application Publication 2016 / 0289559, many of the polysaccharides are branched, although some are substantially unbranched or not heavily branched. Dextran, for example, is characterized by predominantly having λ(1,6) glycosidic linkages between adjacent glucose monosaccharide units, with a limited number of glucose side chains linked to the main polymer structure by D(1,3) glycosidic linkages.Depending on the type of saccharide polymer and its biological source, the extent and location of branching can vary considerably in dextran and other polysaccharides. Throughout the polymer structure, the free hydroxyl groups not involved in glycosidic bond formation in the aforementioned saccharide polymers are predominantly arranged in a trans relationship to one another, specifically as a plurality of trans-neighborly diols positioned along the monosaccharide units that define the polymer structure. Cis-neighborly diols, when present, may reside predominantly at the ends of the polymer structure or within the side chains, if present. A notable exception is guar, which contains a mannose structure with cis-neighborly diols. Certain amine-functionalized polysaccharides described in U.S. Patent Application Publication 2016 / 0289559 can be synthesized via oxidative opening of at least a portion of the monosaccharide rings using sodium periodate, thereby forming a dialdehyde. After dialdehyde formation, reductive amination can be performed to introduce one or more amines into the oxidative opening site. frzannn / zznz / E / Yi The amine functionalization of the oligosaccharides described in U.S. Patent Application 2020 / 0017755 can be carried out in a similar manner. The glycosidic linkages are preserved in the oxidation process, thereby maintaining the structure length of the original saccharin polymer. While the oxidative opening of a portion of the monosaccharide units in saccharide polymers can be successfully carried out with sodium periodate, this reagent may exhibit selectivity for cis-neighborly diols. Many other oxidation reagents are also selective for cis-neighborly diols. As mentioned previously, trans-neighborly diols may predominate along the polymer structure in the aforementioned saccharide polymers, with cis-neighborly diols tending to be located at the ends of the polymer structure or on side-chain branches. Consequently, although effective in promoting oxidative functionalization, sodium periodate may be somewhat limited in the range of amine-functionalized structures it can produce.Specifically, sodium periodate may tend to open cis-neighbor diols in preference to trans-neighbor diols, which can lead to a regional arrangement of amine functionalization after reductive amination. Alternatively, sodium periodate may react with trans-neighbor diols within the polymer structure, but not as completely or effectively compared to the degree of oxidation achievable if a more selective oxidizing reagent for trans-neighbor diols had been available. Specifically, sodium periodate may promote some degree of oxidative opening of trans-neighbor diols within a saccharide polymer, but not to the extent possible (i.e., a higher degree of oxidative opening for post-functionalization at a higher amine loading) if a more selective oxidizing reagent for trans-neighbor diols had been available. Aqueous sodium hypochlorite (i.e., commercial bleach solutions) and sodium hypochlorite pentahydrate, also in aqueous solution, can be very effective oxidizing agents for promoting oxidative cleavage of vicinal diols in saccharide polymers. The latter oxidizing agent can be particularly effective for promoting the oxidative opening of trans-vicinal diols in saccharide polymers, thereby providing access to saccharide polymers with amine functionality that may otherwise be difficult to obtain using other oxidizing agents. In other words, sodium hypochlorite pentahydrate can promote oxidation and subsequent amine functionalization at sites along the saccharide polymer structure that are either unreactive with sodium periodate and similar oxidants that are at least partially selective for the oxidation of cis-vicinal diols.Additionally or alternatively, sodium hypochlorite pentahydrate can promote a greater degree of oxidation and subsequent amine functionalization along the polymer structure than can be achieved with other oxidizing reagents. frzannn / zznz / E / Yi Aqueous solutions of sodium hypochlorite and aqueous sodium hypochlorite pentahydrate can be distinguished at least by differences in their pH. Commercial bleach solutions (aqueous sodium hypochlorite) typically have a pH above approximately 13, whereas aqueous sodium hypochlorite pentahydrate solutions have a pH closer to approximately 10. Consequently, sodium hypochlorite pentahydrate solutions may be advantageous for saccharide polymers that are sensitive to higher pH values. Aqueous sodium hypochlorite solutions are thought to exhibit comparable, but not identical, activity toward trans-vicinal diol cleavage if their pH is adjusted within the same range as that obtained for sodium hypochlorite pentahydrate solutions.As an added advantage over conventional oxidation reagents used to functionalize saccharide polymers, sodium hypochlorite pentahydrate is a considerably less expensive oxidation reagent than sodium periodate. In addition to the above, there may be further differences in reactivity regarding the extent to which overoxidation occurs when monosaccharide units in polysaccharide polymers are oxidized using hypochlorite. Hypochlorite oxidation can produce a limited amount of carboxylic acids when a trans-vicinal diol is oxidatively opened. An aldehyde and a carboxylic acid can be produced at the oxidative opening site in some cases, with the carboxylic acid being retained after reductive amination. Therefore, the present disclosure may allow the introduction of a limited amount of carboxylic acids along the polymer structure.Furthermore, since oxidative opening sites bearing an aldehyde group and a carboxylic acid group can only undergo monofunctionalization when reacted with an amine during reductive amination, the introduction of carboxylic acid can provide a route to fix the amine stoichiometry at the oxidative opening site. In light of the above, sodium hypochlorite pentahydrate can yield different amine-functionalized saccharide polymers than those available with sodium periodate and similar oxidizing agents. These amine-functionalized saccharide polymers may exhibit different properties, particularly with respect to clay stabilization, than those available with sodium periodate. Different amounts and / or locations of amine functionalization can be produced in the products disclosed herein. Furthermore, the potential formation of salt-forming carboxylic acid groups along the saccharide polymer structure may promote additional and complementary clay-stabilizing effects compared to those available with amine-functionalized saccharide polymers formed with other oxidizing agents. Accordingly, the present disclosure provides saccharide polymers with amine functionality comprising one or more monosaccharide units linked by glycosidic bonds and comprising a trans-neighbor diol, wherein the trans-neighbor diol of at least a portion of the one or more monosaccharide units is oxidatively opened and functionalized with at least one amine group at an oxidative opening site. Suitable saccharide polymers may comprise a polysaccharide in some of the embodiments of this disclosure. Polysaccharides and polysaccharides with amine functionality suitable for use in the various embodiments of this disclosure are environmentally safe, substantially non-hazardous to work with, and generally biocompatible. Polysaccharides such as dextran, levan, and guar, for example, as well as their functional forms, may also be biodegradable and pose little or no threat to the environment, even when used in high concentrations. Furthermore, these materials can be obtained or produced at a relatively low cost. Suitable polysaccharides that may be subjected to functionalization in accordance with the disclosure herein include, for example, levan, dextran, guar (guar gum), scleroglucan, welan, pullulan, xanthan (xanthan gum), schizophyllan, cellulose, and any combination thereof. Dextran, levan, and guar may be particularly desirable polysaccharides for use in the formation of the amine-functionalized saccharide polymers disclosed herein. Derivative forms of the foregoing polysaccharides may also be used, and these derivative forms may be subjected to the types of further functionalization described below.Guar derivatives suitable for use in the various forms described in this disclosure may include, for example, carboxyalkyl or hydroxyalkyl derivatives of guar, such as, for example, carboxymethyl guar, carboxymethylhydroxyethyl guar, hydroxyethyl guar, carboxymethylhydroxypropyl guar, ethyl carboxymethyl guar, and hydroxypropylmethyl guar. Similarly, suitable dextran and levan derivatives may include, for example, carboxyalkyl or hydroxyalkyl derivatives of dextran or levan, such as, for example, carboxymethyl dextran (levan), carboxymethylhydroxyethyl dextran (levan), hydroxyethyl dextran (levan), carboxymethylhydroxypropyl dextran (levan), ethylcarboxymethyl dextran (levan), and hydroxypropylmethyl dextran (levan). The polysaccharides suitable for use in the embodiments of this disclosure may cover a wide range of molecular weights. In illustrative embodiments, the molecular weight of suitable polysaccharides may range from approximately 1 million to approximately 50 million daltons. In more specific embodiments, the molecular weight of the polysaccharide, particularly for dextrans and levan, may range from approximately 1 million to approximately 5 million daltons, or from approximately 3 million to approximately 10 million daltons, or from 5 million to approximately 10 million daltons, or from 10 million to approximately 20 million daltons, or from 20 million to approximately 30 million daltons, or from 30 million to approximately 40 million daltons, or from 40 million to approximately 50 million daltons. In addition to polysaccharides, saccharide polymers suitable for use in the disclosure herein may comprise an oligosaccharide having 3 to approximately 20 monosaccharide units, or 3 to approximately 10 monosaccharide units. Oligosaccharides bearing trans-neighbored diols along the polymer structure may provide advantages similar to those achievable with larger saccharide polymers (polysaccharides). Maltodextrin may be a particularly advantageous oligosaccharide for use in the formation of amine-functionalized saccharide polymers of the disclosure herein, particularly those suitable for promoting clay stabilization.Suitable maltodextrins are available in a range of oligomer sizes (e.g., 3–20 glucose monomers), which may allow for some tailoring of clay-stabilizing properties through the selection of the dextrin chain length that undergoes amine functionalization, in accordance with this disclosure. Further tailoring, including adaptation to more effectively stabilize certain types of clay, can be achieved through the selection of the amine used to promote functionalization and the degree of oxidation that takes place. Suitable maltodextrins for forming a saccharide polymer with amine functionality can be obtained from the hydrolysis or pyrolysis of starch, specifically the amylose component of starch, according to non-limiting methods. Furthermore, suitable maltodextrins may exhibit dextrose equivalent values ​​ranging from 3 to approximately 20. In more specific methods, the dextrose equivalent values ​​of maltodextrins may range from approximately 4.5 to approximately 7.0, or from approximately 7.0 to approximately 10.0, or from approximately 9.0 to approximately 12.0. According to this disclosure, saccharide polymers with amine functionality can be formed through the oxidation of a trans-vicinal diol on the monosaccharide units of an original saccharide polymer to form an acyclic structure comprising at least one aldehyde. The oxidative opening may yield a dialdehyde. The at least one aldehyde can be converted to a secondary or tertiary amine group through reductive amination, as shown in Scheme 1 below. Not all oxidative opening sites necessarily undergo amine functionalization in this disclosure.In general, approximately 10 percent or more of the monosaccharide units (counting both unoxidized and oxidatively open monosaccharide units) in the polysaccharide, or approximately 20 percent or more of the monosaccharide units, can be coupled to an amine group in the amine functional group polymers disclosed herein. As such, the amine functional saccharide polymers of this disclosure may contain from zero to two amine groups at each oxidative opening site. Any aldehyde group that remains unfunctionalized after imine formation can be converted to a primary alcohol by reducing the imine portions (imine portions not expressly shown in Scheme 1). Accordingly, each oxidative opening site may comprise from zero to two primary alcohols, depending on the extent to which an imine intermediate was formed.It will be noted that both the monosaccharide ring configuration and the location of the oxidative opening depicted in Scheme 1 are illustrative and not limiting. The R group in Scheme 1 is a hydrocarbyl group, which may be substituted or unsubstituted, linear or branched, and cyclic, acyclic, or aromatic. Scheme 1 frzqnnn / zznz / E / Yi NaOCI*5H2O 1) RNH2 (R “ alkyl or aryl) 2) NaBH4 OH RHN OH OH The oxidative opening of the trans-vicinal diol, shown in Scheme 1 above, can take place in an aqueous solvent or a water-immiscible organic solvent. Suitable aqueous solvents may include water or combinations of water with a water-miscible organic solvent such as acetone, tetrahydrofuran, ethylene glycol, or ethylene glycol dimethyl ether. Suitable water-immiscible organic solvents may include, for example, methylene chloride, toluene, benzene, or similar solvents. When a water-immiscible organic solvent is used, the oxidation reaction can be carried out under two-phase conditions when combined with a solution of sodium hypochlorite pentahydrate. In addition, when using a water-immiscible organic solvent, a phase-transfer catalyst, such as a tetraalkylammonium salt, can be employed. Tetrabutylammonium hydrogen sulfide can be a particularly suitable phase-transfer catalyst. The oxidation reaction with sodium hypochlorite pentahydrate can be carried out at temperatures ranging from approximately 0°C to approximately 50°C. Under normal conditions, the oxidation reaction can be carried out at room temperature (approximately 25°C). As mentioned previously, over-oxidation can occur in some cases when a monosaccharide unit is oxidatively opened with sodium hypochlorite pentahydrate. Over-oxidation can form a carboxylic acid on at least one of the ring-opened carbon atoms. The aldehyde formed during oxidative ring opening can similarly provide an amine intermediate in the presence of the carboxylic acid after exposure to a suitable amine. Instead of being reduced to a primary alcohol after reduction, the carboxylic acid may persist after reduction to form a secondary or tertiary amine, as shown in Scheme 2 below, especially when NaBH4 is used as the reducing agent. Any aldehyde group that does not undergo amine formation may leave a primary alcohol in combination with the carboxylic acid at the oxidative ring opening site. Scheme 2 frzannn / zznz / E / Yi In this disclosure, any primary or secondary amine can be reacted with the partially oxidized saccharin polymer to provide an intermediate amine compound, which subsequently leads to the formation of a secondary or tertiary amine at the oxidative opening site after reduction. Any of the monoamines, diamines, triamines, tetraamines, or even higher polyamines can be attached to the oxidative opening site, according to various modes. The amines suitable for reaction with at least one aldehyde at the oxidative opening site can be either primary or secondary amines. Primary amines lead to the formation of a secondary amine after reductive amination, and secondary amines lead to the formation of a tertiary amine.Suitable amines can otherwise exhibit a variety of structures and can be selected from entities including primary monoamines, secondary monoamines, diamines, triamines and other polyamines, amino alcohols, and the like. Particularly suitable amines may include, but are not limited to, methylamine, dimethylamine, methylethylamine, ethylamine, diethylamine, propylamine, butylamine, hexylamine, octylamine, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetraamine, ethanolamine, and diethanolamine. When more than one amine group is present in the amine, such as in a diamine, a first amine group of the diamine can be directly covalently bonded to a carbon atom at the oxidative opening site, and a second amine group of the diamine can be indirectly bonded to the oxidative opening site. The amine-functionalized saccharide polymers of this disclosure may be coated onto a particle material in some of the embodiments of this disclosure. Suitable particle materials may include a clay material, such as vermiculite, montmorillonite, or bentonite, by way of example. Other suitable particle materials may comprise wood products, including shavings, sawdust, bark, chips, and the like, one or more of which may be compressed together into a granular sediment in some applications. Processed wood particle materials, such as charcoal particles, for example, may also be suitable for use in conjunction with the amine-functionalized saccharide polymers disclosed herein. The amine-functionalized saccharide polymers disclosed herein may be further formulated with a suitable liquid carrier, such as water or a similar aqueous carrier fluid. The amine-functionalized saccharide polymers may have a concentration in the aqueous carrier fluid ranging from approximately 1 wt% to approximately 25 wt%, or from approximately 5 wt% to approximately 20 wt%, or from approximately 5 wt% to approximately 15 wt%, or from approximately 5 wt% to approximately 10 wt%. The aqueous carrier fluid may be derived from any source, including, for example, fresh water, salt water, seawater, groundwater, reflux water, acidified water, aqueous salt solutions, or similar sources. frzonnn / zznz / B / Yii In some embodiments, the amine-functionalized saccharide polymers of this disclosure can be formulated as a subsurface treatment fluid. Treatment fluids can be used in a variety of subsurface treatment operations to facilitate or promote a particular action within the subsurface formation. As used herein, the terms treat, treatment, that treats, and grammatical equivalents refer to any subsurface operation that utilizes a fluid in conjunction with the achievement of a desired function and / or for a desired purpose. Unless otherwise specified, the use of these terms does not imply any particular action by the treatment fluid or a component thereof.Illustrative treatment operations that can be facilitated through the use of the amine-functionalized saccharide polymers of this disclosure include, without limitation, drilling operations, stimulation operations, production operations, remediation operations, sand control operations, and similar operations, which may include, for example, fracturing operations, gravel packing operations, acidizing operations, descaling operations, consolidation operations, workover operations, cleaning operations, and similar operations. Alternatively, the amine-functionalized saccharide polymers of this disclosure may be used in conjunction with underground operations such as, for example, excavation or mining.In particular, saccharide polymers with amine functionality can provide clay stabilization effects during one or more of the above underground treatment operations. As used herein, the term “drilling operation” refers to the process of creating a well borehole in an underground formation. As used herein, the term drilling fluid refers to a fluid used in the drilling of a well borehole. As used herein, the term “stimulation operation” refers to an activity performed within a well borehole to increase its production. As used herein, the term “stimulation fluid” refers to a fluid used downhole during a stimulation activity to increase the production of a subsurface formation resource. In specific cases, stimulation fluids may include fracturing fluid or acidizing fluid. As used herein, the terms “cleaning operation” or “damage control operation” refer to any operation to remove foreign material from a wellbore to increase production. As used herein, the terms cleaning fluid or damage control fluid refer to a fluid used to remove unwanted material from a wellbore that would otherwise block the flow of a desired fluid through it. In one example, a cleaning fluid might be an acidized fluid used to remove material formed by one or more drilling treatments. In another example, a cleaning fluid might be used to remove filter cake from the wellbore walls. As used herein, the term “fracturing operation” refers to a high-pressure operation that creates or extends a plurality of flow channels within a subsurface formation. As used herein, the term fracturing fluid refers to a viscosified fluid used in conjunction with a fracturing operation. As used herein, the term “remediation operation” refers to any operation designed to maintain, increase, or restore a specific production rate from a well, which may include stimulation or cleanup operations. As used herein, the term “remediation fluid” refers to any fluid used in conjunction with a remediation operation. As used herein, the term “acidifying operation” refers to any operation designed to remove acid-soluble material from a wellbore, particularly acid-soluble material comprising at least a portion of the underground formation. As used herein, the term acidizing fluid refers to a fluid used during an acidizing operation. As used herein, the term dewatering fluid refers to a fluid designed for the localized treatment of an underground formation. For example, a dewatering fluid might include a lost circulation material for treating a specific section of the wellbore, such as to seal fractures in the wellbore and prevent subsidence. In another example, a dewatering fluid might include a water control material or a material designed to free a stuck piece of drilling or extraction equipment. As used herein, the term completion fluid refers to a fluid used during the completion phase of a well drilling, which includes cementing compositions and cementing fluids. As used herein, the term cementing fluid refers to a fluid used during cementing operations within a well borehole penetrating an underground formation. The amine-functionalized saccharide polymers described in this disclosure may be present in any of the treatment fluids discussed above. These amine-functionalized saccharide polymers may promote clay stabilization effects when added to any of the treatment fluids. The treatment fluids in this disclosure may have a concentration of the amine-functionalized saccharide polymer ranging from approximately 0.1 gallons (0.378541 L) per thousand gallons (3785.41 L) (gpt) to approximately 10 gpt (37.8541 L), or from approximately 0.5 gpt (1.89271 L) to approximately 5 gpt (18.9271 L), or from approximately 1 gpt (3.78541 L) to approximately 3 gpt (11.3562 L). These concentrations correspond to volume / volume percentages ranging from approximately 0.01% to approximately 1%, or from approximately 0.05% to approximately 0.5%, or from 0.1% to approximately 0.3%. The chosen concentration may vary depending on the particular requirements for a given treatment operation and / or the specific underground conditions found at the bottom of the borehole. Treatment fluids containing amine-functionalized saccharide polymers may optionally also comprise any number of additives, particularly those commonly used in the oilfield services industry. Illustrative additives that may be present in combination with the amine-functionalized saccharide polymers of this disclosure include, for example, surfactants, viscosifiers, gelling agents, gel stabilizers, antioxidants, polymer degradation prevention additives, relative permeability modifiers, scale inhibitors, corrosion inhibitors, chelating agents, foaming agents, defoaming agents, antifoaming agents, emulsifying agents, demulsifying agents, iron control agents, carriers or other particle carriers, particle diverters, salts, acids, fluid loss control additives, gas,Catalysts, other clay control agents, dispersants, flocculants, scrubbers (e.g., H2S scrubbers, CO2 scrubbers, or O2 scrubbers), lubricants, rupturing agents, friction reducers, bridging agents, weighting agents, solubilizers, pH control agents (e.g., buffering agents), hydrate inhibitors, consolidating agents, bactericides, catalysts, and any combination thereof. Suitable examples of these additives will be familiar to a person skilled in the art. As referenced above, the amine-functionalized saccharide polymers of this disclosure can be used in various underground treatment operations to promote clay control or clay stabilization. Promoting clay control or clay stabilization may include one or more of the following: limiting clay swelling or migration of fine clay particles compared to that observed when water or a similarly unmodified aqueous fluid interacts with a clay mineral.In more specific embodiments, the clay stabilization methods of this disclosure may include: providing a clay stabilization composition comprising an amine-functional saccharide polymer of this disclosure; introducing the clay stabilization composition into an underground formation bearing a clay-containing ore; and interacting the amine-functional saccharide polymer with the clay-containing ore to promote clay stabilization. The amine-functional saccharide polymers of this disclosure may promote clay stabilization during any of the underground treatment operations listed above. In more specific applications, the saccharide polymer with amine functionality can be placed in an aqueous carrier fluid when introduced into the underground formation. Suitable aqueous carrier fluids are discussed in more detail above. The aqueous carrier fluid can be introduced into the underground formation at matrix flow rates or at a flow rate that exceeds the fracture gradient pressure of the underground formation. The amine-functionalized saccharide polymers described herein are applicable to the stabilization of a wide range of clays, which may be present in various types of underground formations. Underground formations may contain a clay layer or include a clay-bearing mineral. More specifically, the underground formation undergoing clay stabilization according to this disclosure may be a shale formation. The amine-functionalized saccharide polymers may exhibit a range of clay-stabilizing effects, depending on the nature of the shale formation being treated and the types of clays present. The types of clay that can be stabilized with the amine-functionalized saccharide polymers described in this disclosure include both swollen and unswollen clays. Specific examples of clays that can be stabilized with the amine-functionalized saccharide polymers described in this disclosure include, for example, illite, smectite, illite / mixed smectite, kaolinite, nacrite, dickite, halloysite, chlorite, chamosite, muscovite, biotite, hydrobiotite, talc, glauconite, sepiolite, montmorillonite, nontronite, hectorite, sauconitite, saponite, beidellite, nactrite, endellite, greenosite, palygorskite, vermiculite, and / or attapulgite. In some applications, clay stabilization can be characterized in terms of the capillary suction time observed for a given shale or clay mineral. A decrease in capillary suction time after treatment with amine-functionalized saccharide polymers can be characteristic of clay stabilization. In some specific examples, clay-stabilizing compositions can decrease capillary suction times by approximately 10% to approximately 55% relative to the capillary suction time observed for a given shale or clay mineral in contact with an unmodified aqueous fluid lacking a clay stabilizer. Clay stabilization can also be characterized in terms of the amount of fine particles produced for a given shale or clay mineral when it comes into contact with an aqueous fluid. Effective clay stabilization is characterized by a decreased amount of fine particles produced for a given shale or clay mineral compared to that produced when the shale or clay mineral has been brought into contact with an unmodified aqueous fluid. In some embodiments, the introduction of the clay stabilization composition into the underground formation may include contacting or placing the amine-functionalized saccharide polymer within or on at least one fracture, an area surrounding a fracture, an area designated for fracturing, a flow path, an area surrounding a flow path, a wellbore drilling surface, and / or a nearby wellbore drilling surface. Contacting or placing the clay stabilization composition may involve appropriate fluid diversion techniques in some embodiments. In some methods, clay stabilization compositions can be incorporated into a primary treatment fluid introduced into an underground formation. In other methods, clay stabilization compositions can be incorporated within a fluid pellet introduced before a primary treatment fluid or between two primary treatment fluids. In some or all methods, the introduction of clay stabilization compositions into the underground formation can take place during drilling (i.e., in a drilling fluid) or during completion (e.g., in a cementing fluid). In some methods, clay stabilization compositions can be introduced into the underground formation in conjunction with a hydraulic fracturing operation. The fracturing operation may create or extend at least one fracture or flow path within the underground formation. The introduction or placement of the clay stabilization compositions into the underground formation and the hydraulic fracturing operation can occur at any time relative to each other. In some methods, the clay stabilization compositions may be present within the fracturing fluid, such that clay stabilization occurs simultaneously with or after fracturing. In other methods, the clay stabilization compositions may be present in a cushion fluid introduced into the underground formation prior to the primary fracturing fluid.The primary fracturing fluid may contain a proppant to keep the fractures open, whereas the cushion fluid generally does not contain a proppant. In some or other configurations, clay-stabilizing compositions may be present in an acidizing fluid. These acidizing fluids may include mineral acids or organic acids. Mineral acids may include acids such as hydrochloric acid, hydrobromic acid, or hydrofluoric acid, for example. Organic acids may include, for example, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, or trifluoromethanesulfonic acid. Sufficient quantities of the chosen acid may be present in the acidizing fluid to promote the dissolution of an acid-soluble material in an underground formation or wellbore. The modalities disclosed herein include: A. Compositions comprising a saccharide polymer with amine functionality. The compositions comprise: a saccharide polymer with amine functionality comprising one or more monosaccharide units linked by glycosidic bonds and comprising a trans-neighbor diol, the trans-neighbor diol being of at least a portion of the one or more monosaccharide units being oxidatively open and functionalized with at least one amine group at an oxidative opening site. A1: Compositions comprising a saccharide polymer with amine functionality prepared by a process comprising: exposing a saccharide polymer comprising one or more monosaccharide units linked by glycosidic bonds and comprising a trans-vicinal diol to an oxidizing reagent comprising sodium hypochlorite pentahydrate; reacting the trans-vicinal diol with the oxidizing reagent to form an oxidative opening site bearing at least one aldehyde; exposing the at least one aldehyde to an amine to form an amine intermediate at the oxidative opening site; and reducing the amine intermediate to a secondary or tertiary amine at the oxidative opening site to form a saccharide polymer with amine functionality. B. Methods for oxidizing a saccharide polymer. The methods comprise: exposing a saccharide polymer comprising one or more monosaccharide units linked by glycosidic bonds and comprising a trans-vicinal diol to an oxidizing reagent comprising sodium hypochlorite pentahydrate; reacting the trans-vicinal diol with the oxidizing reagent to form an oxidative opening site bearing at least one aldehyde; exposing the at least one aldehyde to an amine to form an amine intermediate at the oxidative opening site; and reducing the amine intermediate to a secondary or tertiary amine at the oxidative opening site to form a saccharide polymer with amine functionality. C. Methods for treating a subsurface formation with an amine-functional saccharide polymer. The methods comprise: introducing a composition comprising an amine-functional saccharide polymer into a subsurface formation containing a clay-containing ore; and interacting the amine-functional saccharide polymer with the clay-containing ore to promote its stabilization. AC modalities may have one or more of the following additional elements in any combination. Element 1: wherein the amine functional saccharide polymer comprises at least one polysaccharide selected from the group consisting of a dextran, a levan, a guar, and any combination thereof. Element 2: wherein the amine functional saccharide polymer comprises a frzannn / zznz / E / Yi oligosaccharide having from 3 to approximately 20 monosaccharide units. Element 3: wherein the oligosaccharide comprises maltodextrin. Element 4: where the composition also comprises an aqueous carrier fluid. Element 5: wherein the amine functional saccharide polymer carries a secondary amine or a tertiary amine that is directly covalently bonded to one or more oxidative opening sites. Element 6: wherein the amine functional saccharide polymer carries a primary alcohol and the secondary or tertiary amine at one or more oxidative opening sites, or wherein the amine functional saccharide polymer carries a primary alcohol and the secondary or tertiary amine at the oxidative opening site. Element 7: wherein the amine functional saccharide polymer carries a carboxylic acid and the secondary amine or tertiary amine at one or more oxidative opening sites, or wherein the amine functional saccharide polymer carries a carboxylic acid and the secondary amine or tertiary amine at the oxidative opening site. Element 8: wherein the amine-functionalized saccharide polymer comprises one or more oxidative opening sites that are not amine-functionalized. Element 8A: wherein the amine functional saccharide polymer carries two secondary or tertiary amines at one or more oxidative opening sites. Element 9: where at least the majority of the oxidative opening sites are located on monosaccharide units of structure linked by glycosidic bonds. Element 10: where the underground formation comprises a shale formation. By way of non-limiting example, the example combinations applicable to AC include: 1 and 4; 1 and 5; 1 and 6; 1 and 7; 1 and 8; 1 and 8A; 1 and 9; 1, 4 and any combination of 5-8 or 8A; 1 and any combination of 5-8 or 8A; 4 and 5; 4 and 6; 4 and 7; 4 and 8; 4 and 8A; 4 and 9; 5 and 6; 5 and 7; 5 and 8; and 8A; 5 and 9; 6 and 7; 6 and 8; 6 and 8A; 6 and 9; 7 and 8; 7 and 8A; 7 and 9; 8 and 9; 8A and 9; 5-7; 5-8 or 8A; 5-9; 6-8 or 8A; 6-9; 7 and 8; 7 and 8A; 2 and 4; 2-4; 2 and 5; 2 and 6; 2 and 7; 2 and 8; 2 and 8A; 2 and 9; 2, 4 and any combination of 5-8 or 8A; 2 and any combination of 5-8 or 8A; 2, 3 and any combination of 5-8 or 8A; 1 and 2 and 4; 1 and 2 and 3; 1 and 2 and 4; 1 and 2, and 3 and 4; 1 and 2 and 5; 1 and 2 and 6; 1 and 2 and 7; 1 and 2 and 8; and 2 and 8A; 1 and 2 and 9; 1 and 2, and 4 and any combination of 5-8 or 8A; and 1 and 2 and any combination of 5-8 or 8A. Unless otherwise stated, all numbers expressing quantities and the like in this specification and associated claims shall be understood to be modified in all cases by the term "approximately." Accordingly, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the embodiments of the present invention. At least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claim, each numerical parameter shall be interpreted at least in light of the number of significant digits reported and by applying ordinary rounding techniques. One or more illustrative embodiments incorporating various features are presented herein. Not all features of a physical implementation are described or shown in this application for the sake of clarity. It is understood that in developing a physical embodiment incorporating the embodiments of the present invention, numerous implementation-specific decisions must be made to achieve the developer's objectives, such as compliance with system-related, business-related, governance-related, and other constraints, which vary from implementation to implementation and from time to time. While a developer's efforts may be time-consuming, these efforts would nevertheless be a routine task for those skilled in the art who benefit from this disclosure. Whereas various systems, tools, and methods are described herein in terms of “comprising” various components or steps, the systems, tools, and methods may also “consist essentially of” or “consist of” the various components and steps. As used herein, the phrase “at least one of” preceding a list of items, with the terms “and” or “or” separating any of the items, modifies the list as a whole, rather than each individual item. The phrase “at least one of” allows for a meaning that includes at least one of any of the items, and / or at least one of any combination of the items, and / or at least one of each of the items. By way of example, the phrases “at least one of A, B, and C” or “at least one of A, B, or C” each refer to only A, only B, or only C; any combination of A, B, and C; and / or at least one of each of A, B, and C. Accordingly, the disclosed systems, tools, and methods are well suited to achieving the stated purposes and advantages, as well as those inherent therein. The particular embodiments disclosed above are merely illustrative, as the teachings of this disclosure may be modified and implemented in different but equivalent ways evident to those skilled in the art who benefit from the teachings herein. Furthermore, no limitation is proposed on the details of construction or design shown herein, other than as described in the claims below. Accordingly, it is evident that the particular illustrative embodiments disclosed above may be altered, combined, or modified, and all such variations are considered to be within the scope of this disclosure.The systems, tools, and methods disclosed herein for illustrative purposes can be properly implemented in the absence of any element not specifically disclosed herein and / or any optional element disclosed herein. Whereas the systems, tools, and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the systems, tools, and methods may also “consist essentially of” or “consist of” the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower and upper bound is disclosed, any number and any included interval that falls within the range is specifically disclosed.In particular, it should be understood that each range of values ​​(of the form “from approximately aa to approximately b” or, equivalently, “from approximately aab” or, equivalently, “from approximately ab”) disclosed herein sets out each number and interval encompassed within the broader range of values. Furthermore, the terms in the claims have their plain and ordinary meanings unless explicitly and clearly defined otherwise by the patent holder. In addition, the indefinite articles “one” or “an,” as used in the claims, are defined herein as one or more of the elements they introduce. If there is any conflict between the uses of a word or term in this specification and one or more patent documents or other documents that may be incorporated herein by reference, the definitions consistent with this specification shall prevail.

Claims

Having described the present invention, it is considered novel and, therefore, the contents of the following are claimed as property. CLAIMS 1. A composition comprising: a saccharide polymer with amine functionality comprising one or more monosaccharide units linked by glycosidic bonds and comprising a trans-neighbor diol, the trans-neighbor diol being of at least a portion of the one or more monosaccharide units being oxidatively open and functionalized with at least one amine group at an oxidative opening site.

2. The composition of claim 1, wherein the amine functional saccharide polymer comprises at least one polysaccharide selected from the group consisting of a dextran, a levan, a guar, and any combination thereof.

3. The composition of claim 1, wherein the amine functional saccharide polymer comprises an oligosaccharide having from 3 to approximately 20 monosaccharide units.

4. The composition of claim 3, wherein the oligosaccharide comprises maltodextrin.

5. The composition of claim 1, further comprising an aqueous carrier fluid.

6. The composition of claim 1, wherein the amine functional saccharide polymer carries a secondary amine or a tertiary amine that is directly covalently bonded to one or more oxidative opening sites.

7. The composition of claim 6, wherein the amine functional saccharide polymer carries a primary alcohol and the secondary amine or tertiary amine at one or more oxidative opening sites.

8. The composition of claim 6, wherein the amine functional saccharide polymer carries a carboxylic acid and the secondary amine or tertiary amine at one or more oxidative opening sites.

9. The composition of claim 6, wherein the amine-functionalized saccharide polymer comprises one or more oxidative opening sites that are not amine-functionalized.

10. The composition of claim 6, wherein the amine-functionalized saccharide polymer carries two secondary or tertiary amines at one or more oxidative opening sites.

11. The composition of claim 1, wherein at least most of the oxidative opening sites are located on monosaccharide units of structure linked by frzannn / zznz / E / Yi glycosidic bonds.

12. A method comprising: introducing the composition of claim 1 into an underground formation containing a clay-containing mineral; and interacting the amine-functional saccharide polymer with the clay-containing mineral to promote stabilization thereof.

13. The method of claim 12, wherein the underground formation comprises a shale formation.

14. A composition prepared by a process comprising: exposing a saccharide polymer comprising one or more monosaccharide units linked by glycosidic bonds and comprising a trans-vicinal diol to an oxidizing reagent comprising sodium hypochlorite pentahydrate; reacting the trans-vicinal diol with the oxidizing reagent to form an oxidative opening site bearing at least one aldehyde; exposing the at least one aldehyde to an amine to form an amine intermediate at the oxidative opening site; and reducing the amine intermediate to a secondary or tertiary amine at the oxidative opening site to form a saccharide polymer with amine functionality.

15. A method comprising: exposing a saccharide polymer comprising one or more monosaccharide units linked by glycosidic bonds and comprising a trans-vicinal diol to an oxidizing reagent comprising sodium hypochlorite pentahydrate; reacting the trans-vicinal diol with the oxidizing reagent to form an oxidative opening site bearing at least one aldehyde; exposing the at least one aldehyde to an amine to form an amine intermediate at the oxidative opening site; and reducing the amine intermediate to a secondary or tertiary amine at the oxidative opening site to form a saccharide polymer with amine functionality.

16. The method of claim 15, wherein the saccharide polymer comprises at least one polysaccharide selected from the group consisting of a dextran, a levan, a guar, and any combination thereof.

17. The method of claim 15, wherein the saccharide polymer comprises an oligosaccharide having from 3 to approximately 20 monosaccharide units.

18. The method of claim 17, wherein the oligosaccharide comprises a maltodextrin.

19. The method of claim 15, wherein the secondary amine or tertiary amine is directly covalently bonded to the oxidative opening site. frzonnn / zznz / E / Yi 20. The method of claim 19, wherein the saccharin polymer with amine functionality carries a primary alcohol and the secondary amine or tertiary amine at the oxidative opening site.

21. The method of claim 19, wherein the amine functional saccharide polymer carries a carboxylic acid and the secondary amine or tertiary amine at the oxidative opening site.

22. The method of claim 19, wherein the amine functional saccharide polymer carries two secondary or tertiary amines at the oxidative opening site.

23. The method of claim 15, wherein the saccharide polymer with amine functionality comprises one or more oxidative opening sites that are not with amine functionality.