JP2017500234A - In-situ plasticization of polymers for shape change or mechanical property change - Google Patents

Abstract

Using a shape memory polymer to change the physical size and / or mechanical properties of a material, including a method of developing a shape memory polymer having a deformed or compressed shape in an environment at a first temperature A method for deployment and / or plasticization in the field is provided. The method reduces the glass transition temperature of the shape memory polymer from the first glass transition temperature to a second glass transition temperature that is lower than or equal to the first glass transition temperature. It further includes expanding the polymer to expand the shape memory polymer into a deployed shape. [Selection] Figure 2

Description

  The present invention relates to methods and compositions used in oil and gas wells employing shape memory materials, and more particularly, methods for changing the glass transition temperature of shape memory materials using an activated fluid, and And to the composition.

  Shape memory polymers (SMPs) are polymers that regain their original shape when heated above the glass transition temperature (Tg). Forming an article from a shape memory polymer by first fixing the shape by first heating the shape memory polymer to a temperature above the glass transition temperature, then shaping the polymer and subsequently cooling to a temperature below the glass transition temperature . During the development of the article, the article molded to a temperature above the glass transition temperature is heated to regain the originally molded shape.

  Various shape memory polymers (SMPs) have been used in many fields. In particular, SMPs have been used as seal members and filters in downhole environments (eg, oil and natural gas production). However, the deployment of SMPs is accompanied by thermal activation. In thermal activation, the temperature of SMPs is raised to a temperature above the glass transition temperature (Tg) in order to recover the original shape. In order to raise the temperature of SMP to a temperature higher than its Tg, a heated downhole fluid is used as a heat activation medium.

  An alternative to activating SMP articles by heat treatment in a downhole would be highly appreciated in the art.

  In one non-limiting embodiment of the present invention, a method of developing a shape memory polymer is provided that includes disposing a shape memory polymer having a deformed shape in an environment at a first temperature, the shape memory polymer comprising the first memory The first glass transition temperature is higher than the temperature. The method also includes lowering the glass transition temperature of the shape memory polymer from the first glass transition temperature to a second glass transition temperature that is lower than or equal to the first glass transition temperature. The method may include the shape memory in an activation fluid including but not necessarily limited to water, alcohol, aldehyde, amide, amine, carboxylic acid, ester, ether, ketone, dicarbonate, tricarbonate, and combinations thereof. Contacting the polymer. The method also further includes expanding the shape memory polymer to expand the shape memory polymer into an expanded shape.

  In another non-limiting embodiment of the present invention, a method of deploying a shape memory polymer under a downhole environment is provided, the method comprising: deforming a shape memory polymer having a deformed shape under a downhole environment having a first temperature. Including placing. The method also includes contacting the shape memory polymer with an activating fluid to lower the glass transition temperature of the shape memory polymer below the first temperature. The activation fluid can include, but is not necessarily limited to, water, alcohols, glycols, aldehydes, amides, amines, carboxylic acids, esters, ethers, ketones, dicarbonates, tricarbonates, and combinations thereof. In addition, the method extends the shape memory polymer to a deployed shape and removes the activation fluid to maintain the shape memory polymer in the deployed shape by raising the glass transition temperature above the first temperature. Including.

  Furthermore, in another form that does not limit the invention, a system for deploying a shape memory polymer is provided, the system comprising water, alcohol, glycol, aldehyde, amide, amine, carboxylic acid, ester, ether, ketone, diester. An activation fluid selected from the group consisting of carbonates, tricarbonates, and combinations thereof, and a shape memory polymer that is developed by lowering the glass transition temperature in response to contact with the activation fluid.

  The following description should not be construed as limiting the invention in any manner.

It is a graph which shows a time-dependent change of the glass transition temperature of a shape memory polymer. It is a graph which shows the change of the magnitude | size of the diameter of a shape memory polymer with respect to the change of a glass transition temperature. FIG. 6 is a graph showing the magnitude over time of a shape memory polymer in contact with an activated fluid at 105 ° F. (40.5 ° C.). FIG. 5 is a graph showing the magnitude over time of a shape memory polymer in contact with an activated fluid at 110 ° F. (43.3 ° C.). FIG. 5 is a graph showing the magnitude of time for a shape memory polymer in contact with an activated fluid at 115 ° F. (46.1 ° C.). It is a graph which shows the time-dependent change of the outer diameter of a shape memory polymer with high Tg about contact with a certain activated fluid. It is a graph which shows the time-dependent change of the outer diameter of a shape memory polymer with low Tg about contact with a certain activated fluid. It is a graph which shows the time-dependent change of the outer diameter of a shape memory polymer with low Tg about contact with a certain activated fluid.

  Discovery that shape memory polymers can be developed (without increasing the temperature of the environment) by lowering the glass transition temperature (Tg) of the shape memory polymer below that of the environment in which the shape memory polymer is placed. It was done. In this way, by bringing a downhole article comprising a shape memory polymer into contact with an activating fluid to reduce the Tg of the downhole article below the temperature of the downhole surrounding the article, Can be deployed selectively. It has also been discovered that when a shape memory polymer is contacted with an activation fluid, the mechanical properties of the shape memory polymer may alternatively or simultaneously change. Changes in mechanical properties can include, but are not limited to, a decrease in Young's modulus and / or an increase in toughness.

  In one non-limiting embodiment of the invention, the shape memory polymer is recovered from a deformed or compressed shape by contacting the shape memory polymer with an activated fluid that lowers the Tg of the shape memory polymer. It can be developed into a shape.

According to another embodiment not limiting the present invention, the shape memory polymer may be polyurethane, polyurethane made by reaction of polycarbonate polyol and polyisocyanate, polystyrene, polyethylene, epoxy, rubber, fluoroelastomer, nitrile, ethylene propylene Polymers made from diene monomer (EPDM), polyamide, polyurea, polyvinyl alcohol, vinyl alcohol-vinyl ester copolymer, phenolic polymer, polybenzimidazole, N, N'-methylene-bis-acrylamide Cross-linked polyethylene oxide / acrylic acid / methacrylic acid copolymer, polyethylene oxide / methacrylic acid / N-vinyl-2-pyrrolidone copolymer cross-linked with ethylene glycol dimethyl acrylate, ethylene glycol dimethyl acrylate Examples include, but are not necessarily limited to, rate-crosslinked polyethylene oxide / poly (methyl methacrylate) / N-vinyl-2-pyrrolidone copolymers, and combinations thereof. Non-limiting preferred examples include polyurethanes used in Baker Hughes Incorporated's GeoFORM ^™ conformable sand management system.

  According to a non-limiting embodiment, the shape memory polymer contains a base polymer, such as polyurethane. The shape memory polymer is an open cell foam or a solid solid when the polymer is polyurethane. Unlike open cell foam, solid solids are substantially free of pores and / or substantially free of interconnected structures that allow fluid flow through the solid. Generally, polyurethane is a condensate of diisocyanate or polyisocyanate and dihydroxy compound or polyhydroxy compound (sometimes referred to as diol or polyol). Chain extenders (eg, chain extenders based on diamines or polyamines) may be included as an alternative or in addition to the diol instead of part of the diol charge to form the polyurethane. Diols, polyols, diisocyanates, polyisocyanates, chain extenders, and other compounds that react to form polyurethanes are collectively referred to as reactive monomers.

  Examples of dihydroxy compounds and polyhydroxy compounds include diols and polyols having 2 to 30 carbon atoms. Diols suitable for use may include, but are not necessarily limited to, diglycols, triglycols, or glycols containing repeating alkyleneoxy units, including glycols with higher repeating units, ie polyglycols. It is not limited. Suitable diols include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, bishydroxymethylcyclohexane, neopentyl glycol, diethylene glycol, hexanediol, dipropylene glycol, tripropylene Examples include glycol, polypropylene glycol, triethylene glycol, polyethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, and oligomer glycol and polymer glycol such as poly (ethylene-propylene) glycol. It is not limited to these. Combinations having at least one of the dihydroxy compounds can also be used.

  Suitable polyols include, for example, glycerol, trimethylolpropane, pentaerythritol, triols such as tris (2-hydroxyethyl) isocyanurate, tetraols such as dipentaerythritol, and sugars such as inositol, myoinositol, and sorbitol. Although alcohol can be mentioned, it is not necessarily limited to these. Combinations having at least one of the polyhydroxy compounds can also be used.

  Polyurethane can usually be produced by condensation of diisocyanate and diol. Aliphatic polyurethanes having at least two urethane molecular moieties per repeat unit can be used, and the diisocyanate and diol used to make the aliphatic polyurethane are the same. Or a divalent aliphatic group which may be different. The divalent aliphatic unit may be a C2 to C30, particularly C3 to C25, more preferably a C4 to C20 alkylene group, and may be a linear alkylene, branched alkylene, cycloalkylene, and oxyalkylene (polyether alkylene). A heteroalkylene and the like. Suitable aliphatic diradical groups include ethylene, 1,2-propylene and 1.3-propylene, 1,2-butylene, 1,3-butylene, and 1.4-butylene, 1,5-pentamethylene, 1,3- ( 2,2-dimethyl) propylene, 1,6-hexamethylene, 1,8-octamethylene, 1,5- (2,2,4-trimethyl) pentylene, 1,9-nonamethylene, 1,6- (2, 2,4-trimethyl) hexylene, 1,2-, 1,3-, and 1,4-cyclohexylene, 1,4-dimethylenecyclohexane, 1,11-undecamethylene, and 1,12-dodeca Although methylene etc. can be mentioned, it is not limited to these.

  Monomeric diisocyanates can be used to produce polyurethanes. Examples of the diisocyanate component include C4-20 aliphatic diisocyanate or C4-20 aromatic diisocyanate. Suitable aliphatic diisocyanates include isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,7- Heptamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2,2,4-trimethyl-1,5-pentamethylene diisocyanate, 2,2'-dimethyl -1,5-pentamethylene diisocyanate, 3-methoxy-1,6-hexamethylene diisocyanate, 3-butoxy-1,6-hexamethylene diisocyanate, ω, ω'-dipropyl ether diisocyanate, 1,4-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, trimethylhexa Mention may be made of a combination comprising methylene diisocyanate and at least one of the aforementioned compounds.

  Suitable aromatic polyisocyanates include, but are not necessarily limited to, toluene diisocyanate, methylene bis-phenyl isocyanate (diphenylmethane diisocyanate), methylene bis-cyclohexyl isocyanate (hydrogenated MDI), and naphthalene diisocyanate.

  Polymeric or oligomeric diisocyanates can be used together or alternatively to produce polyurethane or urethane or urea-bonded copolymers. Suitable oligomers or polymer chains corresponding to the polymer diisocyanate can include, but are not necessarily limited to, polyurethanes, polyethers, polyesters, polycarbonates, and polyester carbonates. In one non-limiting embodiment, the polyisocyanate is a polymer polyisocyanate such as a polymer chain having an isocyanate group at the end. Examples of polyisocyanates that can be suitably used include polyaliphatic esters including polylactic acid, polyarylated esters including copolymers of phthalate and phenols such as bisphenol A and dihydroxybenzene, and ethylene terephthalate and butylene terephthalate. And the like based on poly (aliphatic-aromatic) esters such as, but not necessarily limited to.

  Diisocyanates based on polyaliphatic esters of the type suitable for use are based on polylactones such as polybutyrolactone and polycaprolactone. Suitable polyester-diisocyanates based on these polyesters include ADIPRENE® LFP 2950A and PP, which are p-phenylene diisocyanate (PPDI) -terminated polycaprolactone prepolymers available from Chemtura. 1096 can be mentioned, but the present invention is not necessarily limited thereto.

  In place of or in addition to the dihydroxy compound, the diisocyanate may be condensed with a diamine that may be referred to as a chain extender. It is understood that the condensation reaction between the diisocyanate and the dihydroxy compound generates a urethane bond in the polymer main chain, while the condensation reaction between the diisocyanate and the diamine generates a urea bond in the polymer main chain. Suitable chain extenders include, but are not necessarily limited to, C4-C30 diamines. The diamine may be an aliphatic diamine or an aromatic diamine. In a specific example, diamines suitable for use include 4,4′-bis (aminophenyl) methane, 3,3′-dichloro-4,4′-diaminodiphenylmethane (4,4′-methylenebis (o-chloro) Aniline) and abbreviated as MOCA.), And aromatic diamines such as dimethyl sulfide toluenediamine (DADMT), but are not necessarily limited thereto.

  In other embodiments that do not limit the present invention, an open cell foam having polyurethane as a base polymer is formed, for example, by a combination of diisocyanates and the diols described herein. A foaming agent may be included to form pores forming an open cell foam. According to one embodiment, when a foaming agent such as water is contained together with a diol, carbon dioxide is generated from the reaction of the diisocyanate and water when the diisocyanate is combined with the water and the diol, thereby obtaining a foam structure. Alternatively, the foam can be formed by other chemical or physical blowing agents. Examples of blowing agents include hydrochlorofluorocarbons (eg, methyl chloride, tetrafluoroethylene, pentafluoropropane, heptafluoropropane, pentafluorobutane, hexafluorobutane, and dichloromonofluoroethane), hydrocarbons (eg, pentane, Isopentane and cyclopentane), carbon dioxide, acetone and water, but are not necessarily limited thereto.

  In a further embodiment that does not limit the present invention, the pores for the open cell foam are opened by letting the components enter a vacuum chamber and letting the gas out of the polymer material by reducing the pressure to a pressure lower than the internal pressure of the polyurethane to be formed. Can be formed.

  The density of the bubbles can be controlled by the amount of water or blowing agent added. The amount of water, based on the weight of the diol (or polyol), is about 0.5 weight percent (wt%) to about 5.0 wt% independently, or about 0.5 wt% to about 4.0 wt% independently In other embodiments, which do not limit the present invention, it can further be about 0.5 wt% to about 3.0 wt% independently. Here, the term “independently” used in conjunction with a numerical range may use any suitable lower limit with any of the above upper limits to form other suitable alternative ranges. Please understand that it means. Instead of, or in addition to, the previous embodiment, the physical blowing agent is about 0.5 wt% to about 0.5 wt% based on the combined weight of the diol (or polyol) and diisocyanate (or polyisocyanate). It can be used independently in an amount of about 15 wt%, alternatively about 0.5 wt% to independently about 10 wt%. In another embodiment that does not limit the present invention, a physical blowing agent such as carbon dioxide can be used in combination with water as the blowing agent.

  According to another embodiment that does not limit the present invention, the composition containing the reactive monomer may be mixed for a certain period of time (eg, about 20 seconds) and then placed in a mold, and an upper metal plate is placed on the mold. Close the mold immediately. Since a large pressure is generated in the bubble forming process, a clasp can be used to hold the upper metal plate and the mold together and prevent the foam from leaking out of the mold. After about 2 hours, the polyurethane foam is sufficiently cured to be removable from the mold, ie, demoldable. Prior to demolding, the shape can be fixed by cooling the mold to a temperature below the glass transition temperature of the polymer. Thereafter, in one embodiment, the polyurethane foam can be post-cured at a temperature of about 100 ° C. for about 6 hours so that the polyurethane foam reaches its maximum strength. Once demolded, the material is a shape memory polymer having an original shape.

  More details about these specific polyurethane foams or polyurethane elastomers can be found in US Pat. No. 7,926,565. Other details regarding polyurethane shape memory materials are described in US Pat. Nos. 7,318,481, 7,828,055, and 8,353,346, assigned to Baker Hughes, Inc.

  The polyurethane foam material may have a “skin” layer on the outer surface of the polyurethane. The epidermis is a layer of solid polyurethane formed when a mixture containing reactive monomers contacts the mold surface. The thickness of the epidermis depends on the concentration of water added to the mixture. Excessive water decreases the thickness of the epidermis, and an insufficient amount of water increases the thickness of the epidermis. The formation of the epidermis is believed to be due to the reaction between the isocyanate in the mixture and the moisture adhering to the mold surface. Thus, an additional mechanical conversion process can be used to remove the epidermis. Tools such as band saws, miter saws, bow saws, and hot filament wires can be used to remove the skin. When the skin is removed from the polyurethane foam material, the polyurethane foam will have a complete open-cell foam structure, excellent elasticity, and very good tear strength. If the polyurethane has an outer skin that needs to be removed, the mold can be of a sufficiently large size to account for material loss due to removal of the skin.

  As an alternative to open cell foam, the polyurethane may be a solid solid that does not have pores interconnecting the cells that are characteristic of open cell foam. Here, for example, reactive monomers can be combined without using a foaming agent, the reaction components are put into a mold, processed, and then demolded as described above to form a solid solid in its original state. Memory polymers can also be produced.

  The shape memory polymer after demolding not only has the original shape but also the original glass transition temperature (Tg), which is a physical characteristic of the material. According to a non-limiting embodiment, once the polyurethane shape memory polymer is demolded in its original form, the shape memory polymer can be reshaped to form a deformed or compressed shape. The shape memory polymer may be subjected to deformation or compression stress by heating to a temperature higher than Tg or close to Tg. Thereafter, the shape memory polymer may be cooled to a temperature lower than its Tg in a state where deformation stress is applied to the shape memory polymer. When cooled to a temperature below the Tg of the shape memory polymer, the polymer is fixed in a deformed shape even when the deformation stress is removed. In order to return to the original shape, the shape memory polymer may be heated again to a temperature higher than Tg or a temperature close to Tg.

  Instead of heating the shape memory polymer and recovering the shape, the method of developing the shape memory polymer is to use a deformed shape memory polymer at a first temperature (the shape memory polymer has a first glass transition temperature, The temperature is higher than the first temperature.) And the glass transition temperature of the shape memory polymer is lower than or equal to the first glass transition temperature from the first glass transition temperature. Lowering to the glass transition temperature and expanding the shape memory polymer to expand the polymer into a developed shape. In one non-limiting embodiment, the shape memory polymer may be a polyurethane. Further, the shape memory polymer may be an open cell foam or a solid solid. Lowering the glass transition temperature of the shape memory polymer includes contacting the shape memory polymer with the activation fluid.

  The glass transition temperature is a physical property of the shape memory polymer and depends in part on the interaction of the constituent polyurethane chains. The glass transition temperature is increased by the strong interaction in the polymer chain of the polyurethane. On the other hand, when the interaction between the polymer chain of the polyurethane and the polymer chain is weak, the glass transition temperature is lowered. It should be understood that the cohesive force of the interaction determines the glass transition temperature of the polyurethane. Thus, since the reactive monomer becomes part of the polymer matrix, the selection of the reactive monomer affects the glass transition temperature. The glass transition temperature of the polyurethane is from about 90 ° C. to about 170 ° C. independently, or from about 95 ° C. to about 160 ° C. independently, and in other embodiments not limiting the present invention, About 100 ° C. to about 150 ° C. independently. As will be described later, the glass transition temperature of polyurethane can be lowered by contact with the activating fluid, resulting in about 5 ° C. to about 70 ° C. independent of this, or about 10 ° C. to independent of this. Further, the glass transition temperature can be lowered in the range of about 60 ° C. The decrease in glass transition temperature is temporary and continues as long as the activating fluid is present in the polyurethane chain. Furthermore, it should be appreciated that shape memory polymers made of polyurethane have substantially the same glass transition temperature and reduced glass transition temperature as polyurethane.

  According to one aspect, the shape memory polymer can be contacted with an activating fluid that reduces the glass transition temperature of the shape memory polymer. The activating fluid can include salt water, solution, and alcohol. In addition, the activation fluid can optionally include a surfactant.

  More specifically, the activating fluid can include water, alcohol, glycol, aldehyde, amide, amine, carboxylic acid, ester, ether, ketone, dicarbonate, tricarbonate, and combinations thereof. Any one of these components can be used by itself. That is, the activation fluid is allowed to contain all of the brine, the activation fluids listed herein, or the solvent (100%), but need not contain all three components.

As defined herein, the water may include salt water. Water or salt water can be used alone. Brine can be included in the composition to change the concentration of the activation fluid and slow the diffusion rate of the activation fluid in the shape memory polymer. Examples of salt water include seawater, associated water, finishing salt water, or a combination thereof. The characteristics of salt water depend on the uniqueness and components of the salt water. As an example, seawater contains a number of components such as sulfate, iodine and trace metals in addition to halide-containing salts. On the other hand, the accompanying water may be water extracted from a production reservoir (for example, a hydrocarbon reservoir) produced from the underground. Accompanying water, also called reservoir brine, often contains a number of components such as barium, strontium, and heavy metals and halogen salts. In addition to naturally occurring salt water (seawater and associated water), fresh water by adding various salts such as NaCl, CaCl ₂ , or KCl to increase the density of salt water to a value of 10.6 lbs / CaCl ₂ salt water It is also possible to synthesize finishing brine. The finishing brine can provide a hydrostatic pressure optimized to counter the reservoir pressure in the downhole. The brine may be modified to include additional salt. In one embodiment, the additional salt to be contained in the brine are _{NaCl, KCl, NaBr, MgCl 2} , CaCl 2, CaBr 2, ZnBr 2, NH 4 Cl, sodium formate, potassium formate, and cesium formate acid. Such salts may be from about 0.5 wt% to about 50 wt% independently, or from about 1 wt% to about 40 wt% independently, based on the weight of the brine, and may limit the invention In other embodiments not, it may be present in the saline in an amount of about 1 wt% to about 25 wt% independently. Brine is usually added so as not to damage the shape memory polymer, either to increase the density of the fluid or to reduce the concentration of chemicals.

  The activation fluid may contain a solvent instead of or in addition to the salt water, which is also referred to as a mutual solvent because it is miscible with two or more liquids. In particular, the mutual solvent is soluble in a hydrophobic liquid and a hydrophilic liquid, for example, soluble in a hydrocarbon fluid and an aqueous solution.

  More specifically, ketones suitable for use include 2-butanone, 2-pentanone, 3-pentanone, acetone, hydroxyacetone, 4-hydroxy-2-butanone, 1-hydroxy-2-butanone, acetylacetone, methyl ethyl ketone. , And combinations thereof, but are not limited thereto. Suitable carboxylic acids for use can include, but are not necessarily limited to, dicarboxylic acids and / or tricarboxylic acids. Suitable dicarboxylic acids for use include, but are not necessarily limited to, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and / or sebacic acid.

Suitable mutual solvents for use include substituted or unsubstituted glycols of the formula R ¹ O (CH ₂ CHR ² O) _n R ³ where R ¹ , R ² and R ³ are independently hydrogen, alkyl groups, aryl And n is from about 1 to about 10), but is not necessarily limited thereto. In other embodiments not limiting the present invention, the alkyl group, aryl group, and acetyl group may have from 1 to about 6 carbon atoms, alternatively from 1 to about 4 carbon atoms. In another embodiment without limitation, it may have from 1 to about 2 carbon atoms. n is 1 to about 10, alternatively 1 to about 6, and in another non-limiting embodiment, 1 to about 3.

  Examples of substituted and unsubstituted glycols include glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, and polyglycol, ethylene glycol monomethyl ether (EGMME), ethylene glycol monoethyl ether (EGMEE), ethylene glycol monopropyl ether (EGMPE), ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (EGMBE), ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl Ether (DEGMME), diethylene glycol monoethyl ether (DEGMEE), diethylene Glycol ethers such as recall mono-n-butyl ether (DEGMBE) and dipropylene glycol monomethyl ether (DPGMEE), dialkyls such as ethylene glycol dimethyl ether (EGDME), ethylene glycol diethyl ether (EGDEE), and ethylene glycol dibutyl ether (EGDBE) Examples include ethers and esters such as ethylene glycol methyl ether acetate (EGMEA), ethylene glycol monoethyl ether acetate (EGMEEA), and ethylene glycol monobutyl ether acetate (EGMBEA), but are not necessarily limited thereto. Combinations comprising at least one of the glycols can also be used.

In one non-limiting embodiment of the invention, the solvent may be a glycol ether, where R ¹ and R ² are both hydrogen, R ³ is a methyl group, an ethyl group, a propyl group, an isopropyl group, and An alkyl group such as a butyl group, and n is 1. In another embodiment, the solvent is ethylene glycol monomethyl ether (EGMME) or ethylene glycol monobutyl ether (EGMBE). Such solvents can be obtained, for example, from Union Carbide Corporation.

Other solvents suitable for use include amides of the formula R ⁴ CONR ⁵ R ⁶ where R ⁴ , R ⁵ and R ⁶ are independently a C1-C5 alkyl group or a C1-C5 alkenyl group And any two substituents of R ^{4 to} R ⁶ may be bonded to form a ring that is contained in 1-methyl-2-pyrrolidone. It is not limited to. Examples of amide solvents include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N, N-dimethylbutyl Amides, 1-methyl-2-pyrrolidone, and 1-ethyl-2-pyrrolidone can be mentioned, but are not limited to these. Such amides are commercially available from, for example, Sigma Aldrich.

  The solvent is not particularly limited as long as the alcohol and the salt water are clearly miscible, and any one of the solvents or a combination including at least one of the solvents can be used.

  The activation fluid can additionally or alternatively contain alcohol. The alcohol may be linear or branched. In one embodiment, the alcohol is a C1-C10 alcohol and includes monohydric alcohols and polyhydric alcohols. Examples of monohydric alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, 2-pentanol, hexanol, octanol , Isooctanol, cyclohexanol, 2-methyl-1-butanol, 2-methyl-1-pentanol, 3-methyl-2-butanol, 2-ethylhexanol, and combinations thereof. It is not limited to. Other alcohols include diols, triols, and polyols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2,4-butanetriol, glycerin, and erythritol. Such polyhydric alcohols can be mentioned, but are not necessarily limited thereto. Combinations of the alcohols can also be used.

  The amount of salt water, solvent, and / or alcohol in the activation fluid will depend on the desired amount and / or diffusion rate of the shape memory polymer as well as the conditions and characteristics of the downhole environment. The activation fluid may include alcohol, the amount of which is from about 2 weight percent (wt%) to about 98 wt%, or about 10 wt%, independently of the weight of the activation fluid. % To independently about 90 wt%, and in one non-limiting embodiment, from about 30 wt% to about 70 wt% independently. The composition may include a solvent, the amount of which is from about 0.05 wt% to about 90 wt% independently, or from about 0.1 wt% to this, based on the weight of the activation fluid. Independently, about 50 wt%, and in other embodiments not limiting the invention, about 1 wt% to about 20 wt%. Again, the activation fluid is preferably pure or made up of 100% of the listed usable ingredients, or water or salt water, or oil and oil-based, water-based, or emulsion-based mud. It should be understood that only diluted ones are suitable for use. Brine may be included in the activation fluid, and the amount is about 20 wt% to about 99 wt% independently, or about 30 wt% to about 30 wt%, based on the weight of the activation fluid. Independently, it can be about 90 wt%, and in a non-limiting embodiment, from about 40 wt% to about 80 wt%.

  Examples of diluents other than water and salt water include, but are not necessarily limited to, water-based mud, oil, oil-based mud, and emulsion-based mud. Suitable oils for use include, but are not necessarily limited to, diesel liquid fuel, LVT 200, diesel oil, LVT-200 oil, polyolefin oil, and synthetic and natural paraffin oils.

  According to one non-limiting aspect of the present invention, the activation fluid contains separate compounds as solvent and alcohol. In another embodiment, the activation fluid contains the same compound as the solvent and alcohol. In one embodiment, the activation fluid contains brine, EGMBE, and / or methanol. More specifically, the activation fluid is about 50 volume percent (vol%) to about 99 vol% brine, about 1 vol% to about 50 vol% EGMBE, and, based on the density of the activation fluid, and About 1 vol% to about 25 vol% methanol can be included.

  Brine, solvent, and / or alcohol may be combined as a composition, or individual components may be used separately as the activation fluid. Alternatively, two of these components may be combined and a third component may be combined later into the resulting two component composition, such as when the activation fluid is introduced into the downhole. The concentration of the activation fluid is about 8 pounds per gallon (ppg) to about 20 ppg independently (about 0.96 to about 2.4 kg / L), or about 9 ppg to about 16 ppg independently (about 1.1 to about 1.9 kg / L), and in other non-limiting embodiments from about 10 ppg to independently about 15 ppg (about 1.2 to about 1.8 kg / L).

  While not wishing to be bound by theory, it is believed that the activating fluid reduces the original glass transition temperature of the shape memory polymer by plasticizing. The activation fluid contains a low molecular weight compound that is smaller than the polyurethane chain of the shape memory polymer, so that the components of the activation fluid penetrate between the molecules of the polyurethane polymer chain and interact with the polyurethane polymer chain, As a result, the cohesive force between the polymer chain and the polymer chain can be reduced. As a result, the mobility of the chain fragments is increased, so that the glass transition temperature is lowered from the original value. As the activation fluid is removed or the concentration of the activation fluid begins to decrease, the Tg of the shape memory polymer increases to its original value prior to contact with the activation fluid. Therefore, it can be said that the effect of the activation fluid on the Tg of the shape memory polymer is temporary. Furthermore, the glass transition temperature does not completely return to the original value (before contact with the activating fluid) and is slightly lower than the original value of the glass transition temperature.

  FIG. 1 shows the time course of the glass transition temperature for a certain shape memory polymer. This shape memory polymer is initially in an environment where the temperature is the first temperature Td, has a shape deformed at time t0, and has a first glass transition temperature Tg1. The first glass transition temperature Tg1 is higher than the first temperature Td. That is, Td <Tg1. With respect to FIG. 1, it should be pointed out that the first temperature Td has not changed, although there may be some variation. At time t1, the activation fluid comes into contact with the shape memory polymer, the glass transition temperature starts to decrease from the first glass transition temperature Tg1, and the glass transition temperature of the shape memory polymer becomes the second glass transition temperature Tg2 (time t2). To fall. Here, Tg2 <Td <Tg3. When the glass transition temperature decreases and becomes smaller than Td, the shape memory polymer operates and changes from its deformed shape to the original shape. At time t3, the activation fluid is removed from the shape memory polymer, and the glass transition temperature starts to rise from the second glass transition temperature Tg2 to the third glass transition temperature T3. When the glass transition temperature becomes higher than Td, the original shape starts to be fixed again to the shape memory polymer. After time t4, the glass transition temperature has reached the third glass transition temperature Tg3, and the shape memory polymer remains in a fixed state in the original shape. As shown in FIG. 1, the third glass transition temperature Tg3 is lower than the first glass transition temperature Tg1. In one embodiment, the third glass transition temperature Tg3 is lower than or the same as the first glass transition temperature Tg1.

  Thus, the polyurethane shape memory polymer can recover its original shape by reducing its glass transition temperature when contacted with an activating fluid. Therefore, thermal activation of the shape memory effect can be avoided. According to the shape recovery by the activated fluid described here, the glass transition temperature of the polyurethane shape memory polymer can be greatly reduced. Instead of heating the shape memory polymer to a temperature that is higher or nearly the same as its original Tg to change it from its deformed shape to its original shape, reducing the Tg of the polyurethane by contacting it with an activating fluid. Thus, the shape can be restored to the original shape.

  In one embodiment, the first glass transition temperature of the shape memory polymer is from about 80 ° C. to independently about 160 ° C., alternatively from about 90 ° C. to about 150 ° C., and in another embodiment not limiting the invention, about 100 ° C. -It can be about 150 degreeC independently. The second glass transition temperature is from about 30 ° C. to about 120 ° C. independently, or from about 35 ° C. to about 110 ° C. independently, and in another embodiment not limiting the present invention, about 40 ° C. C. to about 100.degree. C. independently. In addition, the second glass transition temperature is about 5 ° C to independently about 80 ° C lower than the first glass transition temperature, or about 10 ° C to independently about 70 ° C lower than the first glass transition temperature, In another embodiment that does not limit the present invention, it may be about 10 ° C. to independently about 60 ° C. lower than the first glass transition temperature. The third glass transition temperature is from about 60 ° C. to about 160 ° C. independently, or from about 70 ° C. to about 165 ° C. independently, and in a different embodiment that does not limit the invention, about 80 ° C. -It can be about 150 degreeC independently. Furthermore, the first temperature (ie, the temperature of the environment in which the shape memory polymer is placed) may be about 35 ° C. to about 110 ° C. independently.

  The shape memory polymers described herein can be used in a variety of different applications and are well suited for use in downholes. For example, packer, sand sifting machine, anti-spray device element, submersible pump motor protection device bag, sensor protection device, soccer rod pump, O-ring, T-ring, gasket, soccer rod seal, pump shaft seal, tube seal, valve seal The shape memory polymer can first be molded into an original shape suitable for use as an electrical component seal, electrical component insulation, drill motor seal, drill bit seal, or other downhole element. Before the molded article is inserted into the downhole, the article is deformed at a temperature higher than the Tg of the shape memory polymer and cooled to a temperature lower than the Tg to fix the article in the deformed shape.

  In one aspect, a method for deploying a shape memory polymer in a downhole environment includes placing a shape memory polymer having a deformed shape in a downhole environment at a first temperature. The shape memory polymer may be a downhole element such as a packer or sand sieving machine. In this method, the shape memory polymer is brought into contact with an activating fluid, the glass transition temperature of the shape memory polymer is lowered to a temperature lower than the first temperature, and the shape memory polymer is expanded to an expanded shape and activated. The method further includes removing the fluid to raise the glass transition temperature to a temperature higher than the first temperature, and further maintaining the shape memory polymer in a deployed shape. According to one non-limiting aspect, removing the activation fluid includes replacing the activation fluid with a production fluid, the production fluid comprising a hydrocarbon, a hydrocarbon-containing fluid, an aqueous fluid, or It may be a fluid produced from a downhole environment such as a combination including at least one of these.

  FIG. 2 shows the progression of shape memory polymer (SMP), eg, packer downhaul. The downhole environment (eg, a borehole) has a temperature Td. The SMP in the deformed shape (outer diameter is D2) is placed in the downhole environment at time t0. SMP has a first glass transition temperature Tg1 (> Td). At time t1, the activated fluid contacts the SMP, and the glass transition temperature begins to drop from Tg1. At time t2, the glass transition temperature of SMP becomes substantially equal to Td, and SMP starts to expand from the deformed shape. That is, the outer diameter of SMP increases to a value larger than D2. At time t3, the glass transition temperature has dropped from the first glass transition temperature Tg1 to the second glass transition temperature Tg2, and SMP continues to expand. At time t4, a downhole fluid (eg, hydrocarbon) is produced, the activation fluid is removed from the SMP (or the amount of activation fluid in the SMP is reduced), and the glass transition temperature begins to increase from Tg2. On the other hand, expansion of SMP continues (unless SMP is not fully restored to its original shape, or if it is not in contact with the wall of the borehole or the housing placed in the borehole). At time t5, the glass transition temperature of SMP is approximately equal to Td and the extent of SMP expansion begins to decline (if it continues). At time t6, SMP reaches the third glass transition temperature Tg3, SMP is fixed in its original shape, and seals the excavation hole if used as a packer. By time t6, SMP will be deployed in a downhole environment. Although shown as Tg3 <Tg1 in FIG. 2, the first glass transition temperature Tg1 may be equal to or higher than the third glass transition temperature Tg3. In other words, the final glass transition temperature may be lower than or equal to the original glass transition temperature, and the intermediate glass transition temperature (Tg2 in FIG. 2) is the original glass transition temperature and the final glass transition temperature. Lower than both transition temperatures. The glass transition temperature of SMP is temporarily lowered to a value lower than Td due to the presence of the activation fluid, and the state where the glass transition temperature is lowered to an intermediate value (Tg2 in FIG. 2) is not permanent. Absent.

  In another non-limiting embodiment, the shape memory packer (for placement in a downhole position) is about 60% to about 5% independently of the original shape volume, or about 50%, or about 50%. It is deformed or compressed to have a volume that is about 10% independent of this and about 10% independent of this, and in another embodiment that is not limited to about 40%. In yet another non-limiting embodiment, the shape memory packer is about 50% to about 5% independent of the outer diameter of the original shape, or about 40% to about 5% independently. %, In other embodiments not limiting the invention, it can be deformed or compressed to have an outer diameter that is about 30% to about 5% smaller independently.

  In a different embodiment that does not limit the invention, the shape memory polymer recovers size to at least about 80% of its original size, or at least about 90%, and in other embodiments that do not limit the invention to at least about 99% To do. As used herein, the term “size” of a shape memory polymer means the linear dimension of the active portion of the shape memory polymer. That is, when the shape memory polymer is used as a packer to seal a borehole, the outer diameter is the active part of the shape memory polymer and the outer diameter (OD) is at least about 80% of the original size, or at least In other embodiments that do not limit the invention to about 90%, the size will be restored to at least about 99%.

  According to one non-limiting aspect of the present invention, the rate at which the shape memory polymer expands from a deformed shape to an original shape is at least about 0.3 millimeters per hour (mm / hr) to 12 mm / hr independently, Alternatively, from about 0.4 mm / hr to about 10 mm / hr independently, and in other embodiments not limiting the present invention, from about 0.4 mm / hr to about 8 mm / hr independently.

  The amount of activating fluid used to lower the glass transition temperature to be lower than the downhole temperature is numerous, including the shape memory polymer density and porosity, and downhole characteristics such as temperature and pressure. Depends on the factors. Therefore, the activation fluid will be present in an amount that is effective to lower the glass transition temperature of the shape memory polymer below the downhole temperature. In another non-limiting embodiment, the amount of activation fluid is from about 0.5 vol% of the shape memory polymer to about 100 vol% independently, or from about 0.5 vol% to about 20 independently. vol%, from about 1 vol% to independently about 10 vol% in different embodiments that do not limit the present invention, and from about 3 vol% to about 8 vol independently from other embodiments that do not limit the present invention % Range. Also, the volume ratio of the activation fluid to the shape memory polymer is about 1000: 1 to about 75: 1, alternatively about 4: 1 to about 0.01: 1, and in another embodiment not limiting the invention about 1000: 1 to about 0.01: 1. In other embodiments that do not limit the present invention, the activation fluid may be in the form of vapor or gas, and therefore there is only a much smaller amount of activation fluid compared to the shape memory polymer. In one non-limiting embodiment, the activation fluid is pumped from the ground surface to the target region to temporarily lower the glass transition temperature of the shape memory polymer and develop the shape memory polymer into its original form.

  In other embodiments that do not limit the invention, the shape memory polymer exposure time is approximately instantaneous to independently about 1 year, or about 1 hour to independently about 14 days, without limiting the invention. In another embodiment, it may range from about 6 hours to about 5 days independently.

  Thus, in yet another non-limiting aspect of the present invention, a system for deploying a shape memory polymer comprises an activation fluid containing salt water, a solvent, and / or other activation fluids described elsewhere. And a shape memory polymer that develops as its glass transition temperature decreases in response to contact with the activating fluid. In this system, the shape memory polymer may be an open cell foam such as polyurethane, and the shape memory polymer changes shape from a deformed shape to an expanded shape. The shape memory polymer may be solid such as polyurethane, and the shape changes from a deformed shape to a developed shape.

  The activation fluid may also change the mechanical properties of the shape memory monomer. The changing properties include a decrease in Young's modulus and an improvement in toughness, and both property changes may occur simultaneously, but are not limited thereto.

  Although the foregoing embodiments are further described with respect to particular embodiments of the present invention, they are not intended to limit the invention in any manner and are merely intended to further emphasize or explain the present invention.

(Deformed or compressed shape memory polymer)
A shape memory polymer (SMP) with open cell polyurethane foam was prepared by placing MDI (isocyanate), polycarbonate polyol, and water together in a mold and holding at a temperature above Tg for 18 hours. The mold was cooled to room temperature, and the original SMP was removed. Next, SMP was placed in the cylinder and heated to a temperature higher than or close to the Tg of SMP. The SMP was deformed by compressing the SMP by sandwiching it between two plates in a cylinder to obtain a deformed shape having a volume of 25% of the original volume. The cylinder was cooled to room temperature, and the SMP was removed from the cylinder to produce a deformed SMP.

(Recover shape memory)
The deformed SMP was placed in a container, which was filled with the activation fluid. A linear potentiometer was placed on the top surface of the SMP to acquire data on the expansion of the SMP at the specified temperature, and the displacement of the linear potentiometer recorded the SMP expansion as a function of time.

  For FIGS. 3-5, the activation fluid contained 65 volume percent (vol%) sodium bromide, 25 vol% methanol, and 10 vol% ethylene glycol monobutyl ether (EGMBE). The concentration of activated fluid was 10.7 pounds per gallon (ppg) (1.28 kg / L). Data for SMP expansion was acquired at temperatures of 105 ° F. (40.6 ° C.), 110 ° F. (43.3 ° C.), and 115 ° F. (46.1 ° C.).

  FIG. 3 shows SMP displacement data at 105 ° F. (40.6 ° C.). Here, the SMP height and time are shown in the graph, with the SMP expansion increasing beyond 115 hours. The data obtained show that the extension of three separate SMP samples has been tested and the reproducibility of the measurements is high. Therefore, it can be said that SMP extensions are well defined and can be controlled.

  FIG. 4 shows data for an SMP sample at 110 ° F. (43.3 ° C.), and FIG. 5 shows data for an SMP sample at 115 ° F. (46.1 ° C.).

  FIG. 6 shows SMP displacement data at 185 ° F. (85 ° C.). The activation fluid was oil-based mud (OBM; OMNIFLOW available from Baker Hughes) mixed with 6 vol% methyl ethyl ketone (MEK). The dry Tg of SMP was in the range of 142-148 ° C. (high Tg or HiTg). Here, the outside diameter (OD) versus time of SMP is shown as a graph, and SMP expansion continues for 40 hours.

  FIG. 7 shows the displacement data at 50 ° F. (10 ° C.) of the SMP produced as described above as a graph of the outer diameter of the low Tg shape memory polymer over 70 hours. Here, the activation fluid was 50 vol% (acetone dissolved in water). The dry Tg of this SMP was 98 to 105 ° C. (low Tg or LoTg).

  FIG. 8 shows the displacement data of the SMP produced as described above at 128 ° F. (53 ° C.) as a graph of the outer diameter of the low Tg shape memory polymer over 70 hours. Here, the activation fluid was 9.6 ppg KCl (1.2 kg / L) containing 6 vol% acetylacetone. The dry Tg of this SMP was again 98-105 ° C. (low Tg or LoTg).

  Accordingly, FIGS. 3-8 show that the SMP extension is well defined and controllable.

  While one or more aspects have been shown and described, modifications and substitutions may be made without departing from the scope of the present invention. Accordingly, it should be understood that the present invention has been described by way of illustration and not limitation.

  All ranges disclosed herein include starting and ending values, and the starting and ending points can be combined independently of each other. The expression “(plural)” in parentheses includes a case where there is one or a plurality of items indicated by the term following the notation, that is, there is at least one item indicated by the term. It is used with the intention of being included (for example, “(colorant)” means containing at least one colorant). “Any” or “arbitrary” means that the matter or situation described subsequently may or may not occur, and examples of what happens and what happens Meaning that it contains no examples. The term “combination” as used herein includes blends, mixtures, alloys, reaction products, and the like.

  In addition, the term “a member” or the like without a “plurality” means that the member or the like, unless stated otherwise in the specification, or unless clearly contradicted by context. It does not mean that there is only one, but that there is at least one. The terms such as first and second do not mean the order of importance but are used to distinguish one element from another. The term “about” as used in conjunction with a quantity includes the stated value and has a meaning determined from the context (eg, a certain degree of error associated with the measurement of a particular quantity. Including).

  Since variations and equivalents will be apparent to those skilled in the art, it is further not intended that the invention be limited to the exact details of the illustrated and described structures, operations, materials as described, or aspects. Understood. Accordingly, the invention is limited only by the following claims. Further, the specification is to be construed in an illustrative sense rather than a restrictive sense. For example, a material that makes a polyurethane shape memory material that falls within the parameters set forth in the claims but is not specifically identified or used in a particular method or apparatus, a particular Tg, shape memory Polymers, plasticizers, polymer filter removers, designs and other parts, parts, and structures are expected to be within the scope of the present invention.

  The terms “comprising” and “having” in the claims are to be interpreted as meaning “inclusive” and are not limited to the elements listed.

  The present invention suitably comprises the disclosed elements, suitably comprises the disclosed elements, or suitably substantially comprises the disclosed elements, and is performed in the absence of undisclosed elements. You may be able to. For example, a shape memory polymer having a deformed shape in an environment at a first temperature and having a first glass transition temperature higher than the first temperature is disposed, and water, alcohol, glycol, aldehyde, amide, amine, carvone Contacting the shape memory polymer with an activation fluid selected from the group consisting of acids, esters, ethers, ketones, dicarbonates, tricarbonates, aqueous muds, oils, oil muds, emulsion muds, and combinations thereof. By reducing the glass transition temperature of the shape memory polymer from the first glass transition temperature to a second glass transition temperature lower than or equal to the first temperature, the shape memory polymer is expanded to Shape memory consisting essentially of, or consisting of, developing a shape memory polymer into a developed shape Rimmer can provide a method to deploy.

  Alternatively, a shape memory polymer having a deformed shape in a downhole environment at a first temperature is disposed, water, alcohol, aldehyde, amide, amine, carboxylic acid, ester, ether, ketone, dicarbonate, tricarbonate, and An activated fluid selected from the group consisting of these combinations is brought into contact with the shape memory polymer, the glass transition temperature of the shape memory polymer is lowered below the first temperature, and the shape memory polymer is developed. Extending to a shape memory polymer and consisting essentially of removing the activation fluid to maintain the shape memory polymer in a deployed shape by raising the glass transition temperature above the first temperature, or these A method for developing a shape memory polymer in a downhole environment can be provided.

  Further, in another non-limiting embodiment, the activity selected from the group consisting of water, alcohols, aldehydes, amides, amines, carboxylic acids, esters, ethers, ketones, dicarbonates, tricarbonates, and combinations thereof. A system for deploying a shape memory polymer consisting essentially of or consisting of an activating fluid and a shape memory polymer that is developed by lowering the glass transition temperature in response to contact with the activating fluid. Can be provided.

Claims (19)

Placing a shape memory polymer having a deformed shape in an environment at a first temperature, the shape memory polymer having a first glass transition temperature higher than the first temperature;
Contacting the shape memory polymer with an effective amount of an activating fluid, and the glass transition temperature of the shape memory polymer is less than or equal to the first glass transition temperature from the first glass transition temperature; Lowering to a second glass transition temperature and the activating fluid is selected from the group consisting of water, alcohol, glycol, aldehyde, amide, amine, carboxylic acid, ester, ether, ketone, dicarbonate, tricarbonate, and combinations thereof. Selected
A method of developing a shape memory polymer, comprising expanding the shape memory polymer to expand the shape memory polymer into a developed shape.   The method according to claim 1, wherein the first glass transition temperature is 100C to 150C.   The method according to claim 1, wherein the second glass transition temperature is 40 ° C. to 100 ° C.   The method according to claim 1, wherein the second glass transition temperature is 10 ° C. to 60 ° C. lower than the first glass transition temperature.   The method of claim 1, wherein the first temperature is 60 ° C. to 100 ° C.   The shape memory polymer is polyurethane, polyurethane made by reaction of polycarbonate polyol and polyisocyanate, polystyrene, polyethylene, epoxy, rubber, fluoroelastomer, nitrile, polymer made of ethylene propylene diene monomer (EPDM), Polyethylene oxide / acrylic acid / methacrylic acid copolymer crosslinked with polyamide, polyurea, polyvinyl alcohol, vinyl alcohol-vinyl ester copolymer, phenolic polymer, polybenzimidazole, N, N'-methylene-bis-acrylamide Polyethylene oxide / methacrylic acid / N-vinyl-2-pyrrolidone copolymer crosslinked with ethylene glycol dimethyl acrylate, polyethylene oxide / polyethylene crosslinked with ethylene glycol dimethyl acrylate Methyl methacrylate) / N-vinyl-2-pyrrolidone copolymer, and characterized in that it is selected from the group consisting of combinations of these methods, the method according to any one of claims 1 to 5.   The activation fluid is a group consisting of 2-butanone, 2-pentanone, 3-pentanone, acetone, hydroxyacetone, 4-hydroxy-2-butanone, 1-hydroxy-2-butanone, acetylacetone, methyl ethyl ketone, and combinations thereof. The dicarboxylic acid is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and combinations thereof The method according to claim 1, characterized in that:   The method of claim 1, further comprising: after expanding the shape memory polymer, raising the glass transition temperature of the shape memory polymer to a third glass transition temperature that is higher than the second glass transition temperature. The method described.   The third glass transition temperature is lower than or equal to the first glass transition temperature, but is higher than the first temperature to such an extent that the shape memory polymer maintains the developed shape. The method according to claim 8.   The method according to claim 8, wherein the third glass transition temperature is 80 ° C. to 150 ° C.   6. A method according to any one of the preceding claims, characterized in that the effective amount of the activation fluid is 0.5-100 vol% of the shape memory polymer.   6. A method according to any one of the preceding claims, characterized in that the effective amount of the activation fluid is 1-20 vol% of the shape memory polymer.   The method according to claim 1, wherein the environment is a downhole environment.   The method of claim 1, further comprising removing the activation fluid to maintain the shape memory polymer in the deployed shape by raising the glass transition temperature above the first temperature. 6. The method according to any one of 5 above. An activation fluid selected from the group consisting of water, alcohol, glycol, aldehyde, amide, amine, carboxylic acid, ester, ether, ketone, dicarbonate, tricarbonate, and combinations thereof;
A system for developing a shape memory polymer, comprising: a shape memory polymer that is developed by lowering the glass transition temperature in response to contact with the activating fluid.   The shape memory polymer is polyurethane, polyurethane made by reaction of polycarbonate polyol and polyisocyanate, polystyrene, polyethylene, epoxy, rubber, fluoroelastomer, nitrile, polymer made of ethylene propylene diene monomer (EPDM), Polyethylene oxide / acrylic acid / methacrylic acid copolymer crosslinked with polyamide, polyurea, polyvinyl alcohol, vinyl alcohol-vinyl ester copolymer, phenolic polymer, polybenzimidazole, N, N'-methylene-bis-acrylamide Polyethylene oxide / methacrylic acid / N-vinyl-2-pyrrolidone copolymer crosslinked with ethylene glycol dimethyl acrylate, polyethylene oxide / polyethylene crosslinked with ethylene glycol dimethyl acrylate Methyl methacrylate) / N-vinyl-2-pyrrolidone copolymer, and characterized in that it is selected from the group consisting of a combination of these, the system according to claim 15.   The system of claim 15, wherein the shape memory polymer is an open cell foam having polyurethane, and the shape memory polymer changes shape from a deformed shape to a deployed shape.   The shape memory polymer has a first glass transition temperature, the activation fluid has the effect of lowering the first glass transition temperature to a second glass transition temperature, and the second glass transition temperature is the first glass The system according to claim 15, characterized in that it is 10 ° C. to 60 ° C. below the transition temperature.   The activation fluid is a group consisting of 2-butanone, 2-pentanone, 3-pentanone, acetone, hydroxyacetone, 4-hydroxy-2-butanone, 1-hydroxy-2-butanone, acetylacetone, methyl ethyl ketone, and combinations thereof. The dicarboxylic acid is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and combinations thereof The method according to any one of claims 15 to 18, characterized in that:

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