CN111944164A - Graphene modified degradable material and application thereof - Google Patents
Graphene modified degradable material and application thereof Download PDFInfo
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- CN111944164A CN111944164A CN202010886938.3A CN202010886938A CN111944164A CN 111944164 A CN111944164 A CN 111944164A CN 202010886938 A CN202010886938 A CN 202010886938A CN 111944164 A CN111944164 A CN 111944164A
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- graphene
- glycolic acid
- modified
- acid polymer
- degradable
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a graphene modified degradable material and application thereof. The matrix resin in the raw material components of the degradable material comprises degradable resin and graphene modified glycolic acid polymer. The graphene-modified glycolic acid polymer is obtained by subjecting functionalized graphene and a glycolic acid polymer to a grafting reaction, or subjecting functionalized graphene and a glycolic acid polymer to a physical blending.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and relates to a graphene modified degradable material and application thereof.
Background
At present, in the aspect of drilling and exploitation of oil and gas fields, the staged fracturing technology of a horizontal well is an important means for reforming a main reservoir of a compact oil and gas reservoir at home and abroad and effectively improving the daily yield of a single well. However, the technology of pumping down-hole tools (such as bridge plugs, packers or plugs) for staged fracturing has the problems of long drilling plug period, high construction cost, easy occurrence of down-hole accidents and the like in the later stage of fracturing, and meanwhile, the underground reservoir is easily polluted by debris and operation fluid, so that the down-hole tools made of degradable materials are the primary choice for fracturing construction, and there are many attempts to replace magnesium-aluminum alloy soluble metal materials partially or completely by degradable high polymer materials. With the increasing requirements of people on effective utilization of energy resources and environmental protection, mining conditions such as high depth and the like adopted by people become more and more severe aiming at the mining situation of unconventional resources. However, in the drilling of high-depth underground wells, which are usually in a high-temperature and high-humidity environment, the existing downhole tools made of degradable high polymer materials are subject to such a harsh downhole environment, and the thermal resistance of the downhole tools is insufficient, so that the downhole tools are rapidly degraded undesirably, and the mechanical properties of the downhole tools are remarkably reduced, and the downhole tools are failed.
This can be achieved by introducing materials with superior thermal properties, such as graphene, into the material. Graphene has a two-dimensional hexagonal lattice structure in which a single layer of carbon atoms is densely arranged, and can be regarded as a basic structural unit of a member, such as fullerene, carbon nanotube, or graphite. However, in the application process of compounding graphene and a polymer material, there is a problem that in the dispersion process of graphene, since graphene with an integral structure is composed of a benzene six-membered ring containing a stable bond, the chemical stability is high, the surface is in an inert state, the interaction with other media is weak, and strong intermolecular force exists between each sheet layer of graphene, the sheet layers are very easy to stack together and difficult to disperse, and the graphene is difficult to dissolve in a solvent and difficult to uniformly compound with the polymer material.
Therefore, the development of a degradable material with good graphene dispersibility in the material, good thermal stability and sufficient mechanical properties under high temperature conditions is urgently needed in the field, so that the degradable material can be processed into a downhole tool for temporary plugging fracturing construction under high temperature and high humidity downhole environmental conditions.
Disclosure of Invention
It is an object of the present invention to provide a method for modifying a degradable resin, such as a glycolic acid polymer, by graphene.
The invention also aims to provide a graphene modified degradable material which has good thermal stability and can still maintain enough mechanical properties under high-temperature conditions.
The invention further aims to provide application of the graphene modified degradable material.
In a first aspect of the present invention, there is provided a process for the preparation of a graphene-modified glycolic acid polymer, the process comprising the steps of: carrying out grafting reaction on the functionalized graphene and a glycolic acid polymer to obtain a graphene modified glycolic acid polymer; or
The method comprises the following steps: the functionalized graphene is physically blended with a glycolic acid polymer to obtain the graphene modified glycolic acid polymer.
In another embodiment, the grafting reaction is carried out by starting the monomer for forming the glycolic acid polymer from 130-150 ℃, adding the functionalized graphene when the temperature is raised to 190-205 ℃ by adopting the gradient temperature rise I, and then reacting when the temperature is raised to 210-230 ℃ by adopting the gradient temperature rise II to obtain the graphene modified glycolic acid polymer.
In another embodiment, the gradient temperature rise I is carried out for 1-2 hours at constant temperature by controlling the temperature rise rate to be 1-5 ℃/min and the temperature rise rate to be 20 ℃; and the gradient temperature rise II is to control the temperature rise rate to be 1-2 ℃/min, and the temperature rises by 5 ℃ every time, so that the reaction is carried out for 1-2 hours at constant temperature.
In another embodiment, the charge of functionalized graphene is from 0.1 to 5 wt% of the theoretical mass of glycolic acid polymer obtained, calculated on the mass of monomers forming the glycolic acid polymer; preferably 0.5 to 2 wt%.
In another embodiment, the glycolic acid polymer comprises a glycolic acid homopolymer or/and a glycolic acid copolymer.
In another embodiment, the glycolic acid polymer has a molecular weight of no greater than 10 tens of thousands.
In another embodiment, the functionalized graphene is obtained by:
(i) reacting the functional modifier with graphene oxide to obtain functionalized graphene oxide; the functional modifier is selected from isocyanate modifiers, silane coupling agents or organic amine modifiers; and
(ii) and reducing the functionalized graphene oxide to obtain the functionalized graphene.
In another embodiment, the isocyanate-based modifier comprises a diisocyanate, such as, but not limited to, one of hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, or dicyclohexylmethane diisocyanate;
the silane coupling agents include gamma- (methacryloyloxy) propyl trimethoxysilane (such as, but not limited to, KH-570, A-174, Z-6030), gamma- (2, 3-glycidoxy) propyl trimethoxysilane (such as, but not limited to, KH-560), gamma-aminopropyltriethoxysilane (such as, but not limited to, KH 550).
The organic amine modifier includes an alicyclic amine such as, but not limited to, one of triethylenetetramine, triethylenediamine, or hexamethylenetetramine.
In a second aspect of the present invention, there is provided a graphene-modified glycolic acid polymer obtained by the production method provided by the present invention as described above.
In a third aspect of the present invention, there is provided a graphene-modified degradable material, wherein a matrix resin in raw material components of the degradable material comprises a degradable resin and the graphene-modified glycolic acid polymer provided by the present invention as described above.
In another embodiment, the degradable material contains 2-50 wt% of graphene modified glycolic acid polymer based on the total weight of raw material components of the degradable material; preferably, it contains 10-40 wt%; more preferably, it is contained in an amount of 15 to 30 wt%.
In another embodiment, the degradable material contains 50-100 wt% of matrix resin based on the total weight of the raw material components of the degradable material; preferably, it contains 60 wt% or more; more preferably, it is contained in an amount of 70 wt% or more.
In another embodiment, the degradable resin contained in the base resin has a hydrolyzable functional group selected from one or two or more of the following: ester, amide, hydroxyl, carboxyl, anhydride, and carbamate groups.
In another embodiment, the degradable resin has a molecular weight of not less than 10 ten thousand.
In another embodiment, the degradable resin is selected from at least one or any copolymer, mixture, derivative or combination of aliphatic polyester, polyhydroxy ester ether, polyhydroxy alkanoate, polyanhydride, polyamino acid, polyethylene oxide, polyphosphazene, polyetherester, polyesteramide, polyamide, sulfonated polyester, thermoplastic polyester elastomer or thermoplastic polyurethane elastomer.
In another embodiment, the aliphatic polyester comprises at least one of a hydroxycarboxylic acid aliphatic polyester, a lactone aliphatic polyester, or a diol dicarboxylic acid aliphatic polyester, or any copolymer, mixture, derivative, or combination.
In another embodiment, the aliphatic polyester comprises at least one of polyglycolic acid, polylactic acid, poly-caprolactone, polyethylene succinate, polybutylene succinate, polyethylene terephthalate, or polyethylene adipate, or any copolymer, mixture, derivative, or combination.
In another embodiment, the raw material composition of the degradable material further comprises one or more than two of the following groups: compatilizer, flexibilizer, plasticizer, chain extender, hydrolysis regulation accelerant, hydrolysis regulation inhibitor, heat stabilizer, antioxidant, antibacterial agent and lubricant.
In a fourth aspect of the present invention, there is provided a method for preparing the graphene modified degradable material, which comprises the steps of: the degradable resin and the graphene modified glycolic acid polymer provided by the invention are subjected to melt blending and extrusion to obtain the graphene modified degradable material provided by the invention.
In another embodiment, one or more raw material ingredients comprising the following group are added at the time of melt blending extrusion: compatilizer, flexibilizer, plasticizer, chain extender, hydrolysis regulation accelerant, hydrolysis regulation inhibitor, heat stabilizer, antioxidant, antibacterial agent and lubricant.
In a fifth aspect of the invention, the invention provides an application of the graphene modified degradable material provided by the invention in exploitation operation of oil and gas fields, and the graphene modified degradable material is used for processing and forming a component for a downhole tool.
In another embodiment, the component for a downhole tool is used in production operations of a field.
In another embodiment, the downhole tool is introduced into a subterranean reservoir to be treated in a hydrocarbon field for transient diverting fracturing; degrading the graphene-modified degradable material and producing oil and gas from the underground reservoir.
In another embodiment, the downhole tool comprises at least one of a bridge plug, a packer, or a fracturing ball.
In a sixth aspect of the present invention, there is provided a use of the graphene modified degradable material provided by the present invention as described above in making degradable packaging films, barrier films, mulching films, fibers, plates, sheets, bars or other shaped articles.
Therefore, the invention provides the degradable material with good graphene dispersibility in the material, the thermal stability is good, and the material can still keep enough mechanical properties under the high-temperature condition, so that the material can be processed into an underground tool to be used for temporary plugging and fracturing construction under the high-temperature and high-humidity underground environment condition.
Drawings
Fig. 1 is a schematic structural diagram of a hard glass tube and a pressure water bath tank (mainly composed of a copper tube and a copper nut) used in the degradability test method.
Detailed Description
The inventor conducts extensive and intensive research, and effectively improves the thermal stability of a material system and improves the heat-resisting temperature of the material system by introducing functionalized graphene; in order to improve the dispersibility of graphene in the degradable resin, glycolic acid polymer is selected as an intermediate carrier of graphene, namely, the surface of graphene can be modified to obtain functionalized graphene, and then the functionalized graphene is uniformly pre-dispersed in the glycolic acid polymer by a chemical modification or physical blending method to obtain graphene modified glycolic acid polymer, because the glycolic acid polymer and other degradable resins (with hydrolytic functional groups) generally have relatively good compatibility, a polymer continuous phase in the glycolic acid polymer (as the intermediate carrier) compounded with the functionalized graphene can play a role of a 'compatilizer', which is beneficial for the graphene to be uniformly dispersed in the final material, and can effectively prevent the graphene from being dispersed in the final material with poor uniformity due to agglomeration, and adversely affects the mechanical properties and thermal stability of the final material.
On the basis of this, the present invention has been completed.
Graphene modified glycolic acid polymers
The invention provides a graphene modified glycolic acid polymer, which is characterized in that functionalized graphene is uniformly dispersed in the glycolic acid polymer by modifying the glycolic acid polymer through a chemical grafting method or a physical blending method.
It is noted herein that the relative molecular mass of the glycolic acid polymer can be measured using the following method: glycolic acid polymer was dissolved in hexafluoroisopropanol and formulated into a five parts per million solution for measurement using gel permeation chromatography.
In one embodiment of the present invention, the relative molecular mass of the glycolic acid polymer subjected to graphene modification is not more than 10 ten thousand, and may preferably be 3 to 6 ten thousand, and more preferably 5 ten thousand.
As used herein, a "glycolic acid polymer" is a glycolic acid homopolymer and/or glycolic acid copolymer; preferably, the glycolic acid copolymer is selected to be a copolymer having glycolic acid as the major repeat unit, wherein glycolic acid repeat units (i.e. (-O-CH)2The proportion of-CO-) -) may be selected to be 50 wt% or more, preferably 70 wt% or more, more preferably 85 wt% or more, and still more preferably 90 wt% or more.
According to the present invention, the glycolic acid copolymer contains at least one of a vinyl oxalate-based unit, a hydroxycarboxylic acid-based unit (e.g., a lactic acid unit, a 3-hydroxypropionic acid unit, a 3-hydroxybutyric acid unit, a 4-hydroxybutyric acid unit, a 6-hydroxyhexanoic acid unit, etc.), a lactone-based unit (e.g., a β -propiolactone unit, a β -butyrolactone unit, a γ -butyrolactone unit, -a caprolactone unit, etc.), a carbonate-based unit (e.g., a trimethylene carbonate unit, etc.), or an amide-based unit (e.g., -a caprolactam unit, etc.) in addition to the glycolic acid repeating unit.
As used herein, "Graphene (Graphene)" is a two-dimensional carbon nanomaterial consisting of carbon atoms in sp2 hybridized orbitals in hexagonal honeycomb lattice.
In one embodiment of the present invention, the graphene-modified glycolic acid polymer is prepared by the following steps:
firstly, monomers for preparing a glycolic acid polymer are subjected to polymerization reaction under the action of a catalyst;
in the first step, the polymerization reaction is carried out at about 140 ℃ for about 2 hours, at about 160 ℃ for about 2 hours, at about 180 ℃ for about 2 hours, and at about 200 ℃ for about 1 hour.
In one embodiment of the present invention, a silicone oil solution containing a dispersant, a monomer for producing a glycolic acid polymer, and a catalyst are mixed to perform a polymerization reaction; wherein the dosage relationship of the monomer for preparing the glycolic acid polymer and the silicone oil solution is as follows: the silicon oil solution of 10-20ml contains 1g of monomer for preparing the glycolic acid polymer, the mass fraction of the dispersing agent in the silicon oil solution is 0.1-1%, and the amount of the catalyst is 0.01-0.2% of the mass of the monomer for preparing the glycolic acid polymer.
And secondly, adding an antioxidant and functionalized graphene at about 200 ℃, then heating to about 220 ℃, and continuing to react to obtain the graphene modified glycolic acid polymer.
In the second step, after the functionalized graphene is added, the temperature is raised to about 210 ℃, the pressure is reduced to about-50 kPa gauge, the reaction is carried out for about 1 hour, then the temperature is raised to about 215 ℃, the pressure is reduced to about-90 kPa gauge, the reaction is carried out for about 1 hour, the temperature is raised to about 220 ℃, the pressure is reduced to about-101 kPa gauge, and the reaction is carried out for about 1 hour, so as to fully remove the small molecular substances.
In an embodiment of the present invention, a silicone oil suspension of functionalized graphene is added in the second step, wherein the silicone oil suspension is obtained by ultrasonically dispersing functionalized graphene in silicone oil, and preferably, the silicone oil suspension of functionalized graphene with a mass fraction of 10-30%.
In one embodiment of the invention, the amount of antioxidant is 0.1% to 2% by mass of the monomers used to prepare the glycolic acid polymer; the amount of functionalized graphene used is from 0.1 to 5 wt% of the theoretical mass of glycolic acid polymer obtained, calculated on the mass of monomers used to prepare the glycolic acid polymer.
In one embodiment of the present invention, a third step may be further included, after the reaction is completed, the absolute pressure is controlled to be less than 1kPa, and the temperature is maintained at about 220 ℃ for about 1 hour, discharging and the resultant mass is soaked with petroleum ether several times to remove silicone oil on the surface, and dried (for example, but not limited to, vacuum drying), thereby obtaining the graphene-modified glycolic acid polymer.
In the embodiment of the present invention, the silicone oil used in the above step may be a commercially available methyl silicone oil; the dispersants used may be commercially available fatty alcohol polyoxyethylene ethers such as, but not limited to, MOA-3 or MOA-7; the catalyst employed may be a metal alkoxide such as, but not limited to, stannous octoate; the antioxidant employed may be a commercially available antioxidant 1076, namely n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
The functionalized graphene used in the invention is obtained by modifying the surface of graphene by using a functional modifier, wherein the functional modifier is selected from any one of isocyanate modifiers, silane coupling agents or organic amine modifiers.
As an example, the isocyanate-based modifier may be selected from a diisocyanate, such as, but not limited to, one of commercially available hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, or dicyclohexylmethane diisocyanate, the silane coupling agent may be selected from a silane coupling agent, such as, but not limited to, commercially available gamma-aminopropyltriethoxysilane (such as, but not limited to, KH-550), gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (such as, but not limited to, KH-560), or gamma- (methacryloyloxy) propyltrimethoxysilane (such as, but not limited to, KH-570, A-174, Z-6030), and the organoamine-based modifier may be selected from a cycloaliphatic amine, such as, but not limited to, commercially available triethylenetetramine, tetramine, or dicyclohexylmethane diisocyanate, One of triethylenediamine or hexamethylenetetramine.
According to the invention, the functional modifier is adopted to modify the surface of the graphene so as to prepare the functionalized graphene, and the preparation process can be as follows: firstly, preparing graphene oxide by a Hummers method, then modifying the surface of the graphene oxide by a functional modifier to prepare functionalized graphene oxide, and finally reducing the functionalized graphene oxide to obtain the functionalized graphene. Among them, the functional modifier is preferably a silane coupling agent. Specific preparation steps of functionalized graphene will be exemplified in the detailed description.
Graphene modified degradable material
The invention provides a graphene modified degradable material which comprises degradable resin and a graphene modified glycollic acid polymer compounded with the degradable resin.
In one embodiment of the present invention, the content of the graphene-modified glycolic acid polymer in the material is 2 to 50% by mass, preferably 10 to 40% by mass, and more preferably 15 to 30% by mass.
In one embodiment of the present invention, the degradable resin contained in the graphene-modified degradable material has a hydrolyzable functional group, the hydrolyzable functional group includes at least one of an ester group, an amide group, a hydroxyl group, a carboxyl group, an acid anhydride, or a carbamate group, and the relative molecular mass of the degradable resin is greater than the relative molecular mass of the glycolic acid polymer in the graphene-modified glycolic acid polymer.
In a further embodiment of the present invention, the degradable resin is selected from at least one or any copolymer, mixture, derivative or combination of aliphatic polyester, polyhydroxyester ether, polyhydroxyalkanoate, polyanhydride, polyamino acid, polyethylene oxide, polyphosphazene, polyetherester, polyesteramide, polyamide, sulfonated polyester, thermoplastic polyester elastomer or thermoplastic polyurethane elastomer; wherein the aliphatic polyester comprises at least one of hydroxycarboxylic acid aliphatic polyester, lactone aliphatic polyester or diol dicarboxylic acid aliphatic polyester or any copolymer, mixture, derivative or combination thereof, preferably, the aliphatic polyester is selected from at least one of polyglycolic acid, polylactic acid, poly-caprolactone, polyethylene succinate, polybutylene succinate, polyethylene terephthalate or polyethylene adipate or any copolymer, mixture, derivative or combination thereof, more preferably, the aliphatic polyester is preferably polyglycolic acid.
In an embodiment of the present invention, the graphene-modified degradable material further includes at least one of a compatibilizer, a toughener, a plasticizer, a chain extender, a hydrolysis regulation promoter, a hydrolysis regulation inhibitor, a heat stabilizer, an antioxidant, an antibacterial agent, or a lubricant.
In a more specific embodiment of the invention, the compatibilizer may be selected from commercially available maleic anhydride grafted compatibilizers. Further, in terms of the amount, the weight part of the compatilizer is 0.1-5 parts based on 100 parts of the graphene modified degradable material.
In a more specific embodiment of the present invention, the toughening agent is a degradable toughening agent, and can be selected from at least one of commercially available polybutylene succinate, polybutylene terephthalate-adipate, polybutylene succinate-adipate or polymethyl ethylene carbonate. Further, in terms of usage amount, the weight part of the toughening agent is 0.1-20 parts based on 100 parts of the graphene modified degradable material.
In a more specific embodiment of the present invention, the plasticizer may be selected from at least one of commercially available glycerin, epoxidized soybean oil, epoxidized butyl furoate, or acetyl tributyl citrate. Further, in terms of the amount, the weight part of the plasticizer is 0.1-5 parts based on 100 parts of the graphene modified degradable material.
In a more specific embodiment of the present invention, the chain extender may be selected from at least one of the commercially available epoxy chain extenders ADR, maleic anhydride or glycidyl methacrylate. Further, in terms of the amount, the weight part of the chain extender is 0.1-1 part based on 100 parts of the graphene modified degradable material.
In a more specific embodiment of the present invention, the hydrolysis regulation accelerator may be selected from substances that are themselves rapidly hydrolyzable and that produce an organic acid upon hydrolysis, for example, may be selected from dimethyl oxalate or diethyl oxalate, and the organic acid produced by hydrolysis may be effective to accelerate hydrolysis of the degradable resin matrix. Further, in terms of the amount, the hydrolysis regulation accelerant is 0.1-3 parts by weight based on 100 parts by weight of the graphene modified degradable material.
In a more specific embodiment of the invention, the hydrolysis regulation inhibitor may be selected from substances that react with the hydrolysis product carboxylic acid or water to prevent degradation from the catalyzed hydrolysis from occurring, for example, may be selected from carbodiimides. Further, in terms of the amount, the hydrolysis regulation inhibitor is 0.1 to 3 parts by weight based on 100 parts by weight of the graphene modified degradable material.
In a more specific embodiment of the present invention, the heat stabilizer may be selected from at least one of commercially available calcium fatty acid soaps (e.g., calcium stearate soap, calcium oleate soap, calcium palmitoleate soap, calcium linoleate soap, etc.) or zinc fatty acid soaps (e.g., zinc stearate soap, zinc palmitate soap, zinc oleate soap, etc.). Further, in terms of the amount, the weight part of the heat stabilizer is 0.1-4 parts based on 100 parts of the graphene modified degradable material.
In a more specific embodiment of the present invention, the antioxidant may be selected from at least one of commercially available antioxidants 168, 1010, 1076, 264, 1024, B215 or 225. Further, in terms of the using amount, the weight part of the antioxidant is 0.1-3 parts based on 100 parts of the graphene modified degradable material.
In a more specific embodiment of the present invention, the antimicrobial agent may be selected from at least one of commercially available paraformaldehyde, peroxyacetic acid, or polyquaternium. Further, in terms of the amount, the weight part of the antibacterial agent is 0.1-1 part based on 100 parts of the graphene modified degradable material.
In a more specific embodiment of the present invention, the lubricant may be selected from at least one of commercially available talc, polyethylene wax, or ethylene bis stearamide. Further, in terms of the amount, the weight part of the lubricant is 0.1-3 parts based on 100 parts of the graphene modified degradable material.
According to the invention, a filler can be added into the graphene modified degradable material according to actual requirements, the filler can have hygroscopicity or water solubility, and can be used for accelerating the permeation of external water to a material matrix, so that the degradation of the matrix is facilitated, and the degradation speed of the material can be adjusted by matching with a hydrolysis adjustment promoter and a hydrolysis adjustment inhibitor. Fillers meeting the above characteristics may be chosen, for example, from NaCl, CaCl2、MgCl2、Na2CO3、KH2PO4Or sodium benzenesulfonate, etc.; in addition, the fillers may also be selected from metal oxides or metal hydroxides or metal carbonates, for example CaO, ZnO, CuO, Al2O3、MgO、Ca(OH)2Or Mg (OH)2Etc. these substances can generate hydroxide ions or other strong nucleophiles when contacting with water, and can also be used for improving the rate of water penetration into the material, thereby influencing the degradation rate of the material; the filler can also be selected from kaolin, quartz powder or diatomite. Preferably, the particle size of the filler can be chosen to be from 10 nm to several hundred nm or even several hundred microns, for example 10-800 nm or 10 nm-500 microns. Further, in terms of the amount, the weight part of the filler is 0.5 to 20 parts, preferably 5 to 12 parts, based on 100 parts of the graphene modified degradable material.
According to the present invention, for the degradable resin compounded with the graphene-modified glycolic acid polymer employed in the material, a degradable resin having a relatively high molecular mass, for example, a degradable resin having a relatively molecular mass of not less than 10 ten thousand, for example, 10 ten thousand to 100 ten thousand, preferably 15 to 65 ten thousand, or further, a degradable resin having a relatively molecular mass of not less than 20 ten thousand, for example, 20 to 30 ten thousand, may be selected, taking the mechanical properties and thermal stability of the resulting material into consideration. The degradable resin with relatively large molecular mass is selected, and the degradable resin has good mechanical strength, which can play an important role in the final mechanical property of the material.
The graphene modified degradable material provided by the invention can be prepared by a method commonly used in the art, such as but not limited to, melt blending and extruding a degradable resin and a graphene modified glycolic acid polymer compounded with the degradable resin.
In an embodiment of the present invention, during the melt blending and extrusion, additives such as a compatibilizer, a toughener, a plasticizer, a chain extender, a hydrolysis control promoter, a hydrolysis control inhibitor, a heat stabilizer, an antioxidant, an antibacterial agent or a lubricant may be added as appropriate according to actual needs to further improve the performance of the material.
The invention also provides application of the graphene modified degradable material, wherein the graphene modified degradable material is processed into a component for a downhole tool and is used for exploitation operation of oil and gas fields.
In one embodiment of the invention, the downhole tool may be introduced into a subterranean reservoir to be treated in a field of oil and gas, subjected to transient diverting fracturing; degrading the material and producing hydrocarbons from the subterranean reservoir.
In one embodiment of the invention, the downhole tool comprises at least one of a bridge plug, a packer, or a fracturing ball.
According to the present invention, a molded article can be obtained by a conventional molding method such as extrusion molding, injection molding, calender molding, blow molding, etc. using the graphene-modified degradable material of the present invention, and the molded article (which may be referred to as a "primary molded article") can be subjected to machining such as cutting, boring, cutting, etc. to obtain a molded article (which may be referred to as a "secondary molded article") having a desired shape.
It should be noted that the graphene modified degradable material of the present invention can be used for manufacturing degradable packaging films, barrier films, mulching films, fibers, plates, sheets, bars or other shaped articles, besides being applied to downhole operations.
The features mentioned above with reference to the invention, or the features mentioned with reference to the embodiments, can be combined arbitrarily. All features disclosed in this specification may be combined in any combination, provided that there is no conflict between such features and the combination, and all possible combinations are to be considered within the scope of the present specification. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
The main advantages of the invention are:
the component for the downhole tool, which is processed by the graphene modified degradable material provided by the invention, can still maintain enough mechanical strength under a high-temperature condition, can be used for temporary plugging diversion fracturing construction in a high-temperature high-humidity downhole environment, can be easily removed after being degraded for a period of time in the downhole environment according to the actual application requirements, and cannot influence an underground reservoir stratum, so that the downhole construction efficiency is improved, and the construction cost is reduced.
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. For example, "a range of from 1 to 10" should be understood to mean every and every possible number in succession between about 1 and about 10. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific points, it is to be understood that any and all data points within the range are to be considered explicitly stated.
As used herein, the term "about" when used to modify a numerical value means within + -5% of the error margin measured for that value.
The glycolic acid polymers used in the present invention include glycolic acid homopolymers and/or glycolic acid copolymers, which may be commercially available products or may be self-made, for example, with respect to glycolic acid homopolymers, obtainable by methods known to those skilled in the art for the preparation of polyglycolic acid, i.e. by direct condensation of glycolic acid or by catalytic ring-opening polymerization of cyclic glycolides, and will not be described herein in detail.
The glycolic acid copolymer may further include, in addition to the glycolic acid repeating unit, at least one of a vinyl oxalate unit, a hydroxycarboxylic acid unit (e.g., a lactic acid unit, a 3-hydroxypropionic acid unit, a 3-hydroxybutyric acid unit, a 4-hydroxybutyric acid unit, a 6-hydroxyhexanoic acid unit, etc.), a lactone unit (e.g., a β -propiolactone unit, a β -butyrolactone unit, a γ -butyrolactone unit, a caprolactone unit, etc.), a carbonate unit (e.g., a trimethylene carbonate unit, etc.), or an amide unit (e.g., -caprolactam unit, etc.). In addition, the glycolic acid repeat unit (i.e. (-O-CH) in the glycolic acid copolymer2The proportion of-CO-) -) may be preferably 50 wt% or more, more preferably 70 wt% or more, further preferably 85 wt% or more, and most preferably 90 wt% or more.
The degradable resin in the material of the present invention may be selected from glycolic acid polymers, and may be selected from other degradable resins than glycolic acid polymers. In the present invention, the degradable resin means, for example, a degradable polymer having a biodegradable property or a hydrolytic property, wherein the biodegradable property means that it can be decomposed by downhole microorganisms and the hydrolytic property means that it can be decomposed by downhole liquid, particularly by water, more preferably water containing an acid or an alkali. In addition, the resin is weak due to its low degree of polymerization or the like, and as a result, it can be easily disintegrated to lose its original shape by applying a very small mechanical force, and such a resin also conforms to the degradable polymer.
[ preparation of graphene oxide ]
The invention can adopt Hummers method to prepare graphene oxide, for example, the following steps can be adopted:
2g of graphite and 1g of NaNO346ml of 98% concentrated sulfuric acid, the mixture was placed in an ice-water bath, stirred for 30 minutes to mix the mixture sufficiently, and 6g of KMnO was weighed4Adding into the above mixed solution for several times, stirring for 2 hr, transferring into 35 deg.C warm water bath, and stirring for 30 min; slowly adding 92ml of distilled water, controlling the temperature of the reaction liquid to be about 98 ℃ for 15 minutes, and adding a proper amount of 30% H2O2Removing excessive oxidant, diluting with 140ml distilled water, filtering while hot, sequentially washing with 0.01mol/L HCl, anhydrous ethanol and deionized water until there is no SO in the filtrate4 2-Until the graphite exists, preparing graphite oxide; then ultrasonically dispersing graphite oxide in water to prepare a dispersion liquid of graphene oxide; and (3) drying the dispersion liquid of the graphene oxide in a vacuum drying oven at 60 ℃ for 48 hours to obtain a graphene oxide sample, and storing for later use.
[ preparation of functionalized graphene oxide ]
Taking silane coupling agent KH-570 as an example, the functionalized graphene oxide can be prepared by the following steps:
weighing 100mg of graphene oxide in 60ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 1 hour to form a uniform dispersion liquid; adding a certain amount of HCl, and adjusting the pH value of the dispersion liquid to 3-4; then, 10ml of 95% ethanol solution containing 0.3g of KH-570 is slowly added under stirring, the reaction is continued for 24 hours at the temperature of 60 ℃, centrifugal separation is carried out, and the mixture is washed with absolute ethanol and deionized water for multiple times to remove unreacted KH-570, and the washing liquid is made to be neutral, thus obtaining the functionalized graphene oxide.
Taking hexamethylene diisocyanate as an example of an isocyanate modifier to prepare functionalized graphene oxide, the following steps can be adopted:
weighing 50mg of graphene oxide, ultrasonically dispersing the graphene oxide in 100ml of DMF (namely N-N dimethylformamide) for 30 minutes, then adding 2.5g of hexamethylene diisocyanate and 5 drops of catalyst DBTDL (namely dibutyltin dilaurate), heating to 90 ℃, and stirring to react for 24 hours; after the reaction is finished, washing for multiple times by using ethanol and performing centrifugal separation to obtain the functionalized graphene oxide.
Taking triethylenetetramine as an organic amine modifier as an example, the following steps can be adopted to prepare functionalized graphene oxide:
weighing 200mg of graphene oxide, ultrasonically dispersing in 200ml of DMF (N-N dimethylformamide) for 2.5 hours to obtain a graphene oxide suspension, adding 30g of triethylenetetramine and 5g of dicyclohexylcarbodiimide, ultrasonically treating for 5 minutes, reacting at 120 ℃ for 48 hours, adding 60ml of absolute ethyl alcohol, and standing overnight; and removing the supernatant, filtering the lower precipitate by using a polytetrafluoroethylene membrane, and washing the lower precipitate for multiple times by using absolute ethyl alcohol and deionized water to obtain the functionalized graphene oxide.
[ preparation of functionalized graphene ]
The present invention can reduce functionalized graphene oxide to functionalized graphene with a suitable reducing agent (e.g., hydrazine hydrate), for example, the following steps can be employed:
dispersing the washed and undried functionalized graphene oxide in 60ml of absolute ethyl alcohol, performing ultrasonic dispersion for 1 hour to form uniform and stable functionalized graphene oxide dispersion liquid, then adding 1g of hydrazine hydrate, and reducing for 24 hours at 60 ℃; and washing the obtained product to be neutral by using absolute ethyl alcohol and deionized water, and drying the product in a vacuum drying oven at the temperature of 60 ℃ for 48 hours to obtain the functionalized graphene, and storing for later use.
It should be understood that the preparation method of the functionalized graphene according to the present invention is not limited to the description in the above examples, and other suitable methods may be adopted to modify the surface of the graphene.
[ preparation of graphene-modified glycolic acid Polymer ]
The glycolic acid polymer modified by the graphene used in the invention can be prepared by bonding functionalized graphene and the glycolic acid polymer through a chemical reaction, or prepared by physically blending functionalized graphene and the glycolic acid polymer.
The method of the first step can be realized by taking a functionalized graphene-modified glycolic acid homopolymer as an example, through the following steps:
step 1): ultrasonically dispersing functionalized graphene in silicone oil, and preparing a silicone oil suspension of the functionalized graphene with the mass fraction of 10-30%;
step 2): adding a silicone oil solution containing a dispersing agent into a stirring reactor, then adding a glycolic acid monomer and a catalyst, starting reaction at 140 ℃, then carrying out gradient heating to 200 ℃, then sequentially adding an antioxidant and the functionalized graphene silicone oil suspension prepared in the step 1), then carrying out gradient heating to 220 ℃, and carrying out pressure reduction for continuous reaction to remove small molecular substances;
step 3): and after the reaction is finished, controlling the absolute pressure in the stirring reactor to be less than 1kPa, maintaining the temperature of the stirring reactor at 220 ℃ for 1 hour, then discharging, soaking the obtained material with petroleum ether for multiple times to remove silicone oil on the surface, and then carrying out vacuum drying to obtain the graphene modified glycolic acid homopolymer.
Wherein, the dosage relationship of the glycolic acid monomer and the silicone oil solution in the step 2) is as follows: each 10-20ml of the silicone oil solution contains 1g of glycolic acid monomer. The mass fraction of the dispersant in the silicone oil solution is 0.1-1%, the dosage of the catalyst is 0.01-0.2% of the mass of the glycolic acid monomer, and the dosage of the antioxidant is 0.1-2% of the mass of the glycolic acid monomer.
The amount of functionalized graphene used in step 2) is from 0.1 to 5% by weight, based on the mass of glycolic acid monomer, of the theoretical mass of glycolic acid homopolymer obtained.
The silicone oil used in the above step may be commercially available methyl silicone oil; the dispersants used may be commercially available fatty alcohol-polyoxyethylene ethers, for example MOA-3 or MOA-7; the catalyst used may be a metal alkoxide, such as stannous octoate; the antioxidant employed may be a commercially available antioxidant 1076, namely n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
In addition, in the step 2), glycolic acid monomer is subjected to polymerization reaction under the action of a catalyst, the polymerization reaction is carried out for 2 hours at 140 ℃, the temperature is raised to 160 ℃ for reaction for 2 hours, then the temperature is raised to 180 ℃ for reaction for 2 hours, and the temperature is raised to 200 ℃ for reaction for 1 hour;
after the functionalized graphene silicon oil suspension is added, firstly heating to 210 ℃, reducing the pressure to the gauge pressure of-50 kPa, reacting for 1 hour, then heating to 215 ℃, reducing the pressure to the gauge pressure of-90 kPa, reacting for 1 hour, then heating to 220 ℃, reducing the pressure to the gauge pressure of-101 kPa, and reacting for 1 hour to fully remove the small molecular substances.
By adopting the method of the first step, the polymer in the prepared graphene modified glycolic acid homopolymer is a low molecular weight glycolic acid homopolymer, and the relative molecular mass of the polymer is not more than 10 ten thousand.
It is noted herein that the relative molecular mass of the glycolic acid polymers of the present invention can be measured by the following method: glycolic acid polymer was dissolved in hexafluoroisopropanol and formulated into a five parts per million solution for measurement using gel permeation chromatography.
The method of (c) may be a method of physically blending the functionalized graphene with a glycolic acid polymer (which may be a glycolic acid homopolymer, a glycolic acid copolymer, or a glycolic acid homopolymer and a glycolic acid copolymer) by using a conventional mixer, and the present invention may be a method of blending the functionalized graphene with a glycolic acid polymer by using a technical scheme known to those skilled in the art without any particular limitation on the blending parameters (for example, time, temperature, stirring speed, etc.). Meanwhile, the specification and parameters of the mixer are not particularly limited, and the technical scheme known by the technical personnel in the field when the mixer is used for mixing can be adopted.
The glycolic acid polymer used in the physical blending method is also preferably selected to be a polymer having a molecular weight of not more than 10 ten thousand, and the glycolic acid polymer having a molecular weight of not more than 10 ten thousand can itself be used as a graphene-supporting carrier and also as a compatibilizer.
[ preparation of graphene-modified degradable Material ]
The graphene-modified glycolic acid polymer described above is melt-blended and extruded with a glycolic acid polymer of high molecular weight (for example, a relative molecular mass of 10 to 100 ten thousand, preferably 15 to 65 ten thousand, and more preferably 20 to 30 ten thousand) and/or a degradable resin other than the glycolic acid polymer to produce a graphene-modified degradable material.
Here, taking the melt blending extrusion of the graphene-modified glycolic acid polymer and the high molecular weight glycolic acid polymer as an example, the process conditions of the melt blending extrusion may be: the temperature is set to 150 ℃ along the supply part to the discharge part of the extruder, the temperature of each section from the 1 st zone to the 13 nd zone is respectively controlled within the range of 190 plus 230 ℃, the screw rotating speed is controlled to be 180 plus 350rad/min, the feeding rotating speed is controlled to be 10-30rad/min, the vacuum degree is controlled to be-0.06 MPa to-0.08 MPa, and the traction speed is controlled to be 5-30 m/min.
During the melt blending extrusion, auxiliary agents such as a compatilizer, a flexibilizer, a plasticizer, a chain extender, a hydrolysis regulation accelerant, a hydrolysis regulation inhibitor, a heat stabilizer, an antioxidant, an antibacterial agent or a lubricant can be properly added according to actual requirements so as to further improve the performance of the material.
The graphene modified degradable material of the invention is further illustrated by specific examples.
The components and their dose relationships for the graphene-modified degradable materials of examples 1-15 are listed in table 1 below.
TABLE 1 composition and amount of graphene-modified degradable material
In table 1, the graphene-modified glycolic acid polymers in examples 1 to 12 are prepared by a method of bonding functionalized graphene and a glycolic acid homopolymer through a chemical reaction, and can be specifically described with reference to the procedure of the method of (i) above; the graphene-modified glycolic acid polymers in examples 13-15 were prepared by a physical blending method of functionalized graphene and glycolic acid polymer; among the graphene-modified glycolic acid polymers used in example 13, the glycolic acid polymer was a copolymer of glycolic acid and lactic acid (i.e., polyglycolic acid-lactic acid, PGLA for short), and the proportion of glycolic acid repeating units was about 92 wt%; example 14 employed a graphene-modified glycolic acid polymer wherein the glycolic acid polymer was a copolymer of glycolic acid and-caprolactam with a proportion of glycolic acid repeat units of about 85 wt%; example 15 the graphene-modified glycolic acid polymer used was a copolymer of glycolic acid and trimethylene carbonate, and the proportion of glycolic acid repeating units was about 90 wt%.
For the preparation of the graphene modified glycolic acid polymers in each example, see table 2 for the charge of functionalized graphene (note: in examples 1-12, the charge of functionalized graphene is calculated based on the theoretical mass of glycolic acid homopolymer calculated from glycolic acid monomer) and the relative molecular mass of the corresponding glycolic acid polymer obtained.
TABLE 2 charge of functionalized graphene and relative molecular mass of the corresponding glycolic acid polymer
Examples 1-15 component species of graphene-modified degradable materials are shown in table 3 below.
TABLE 3 component classes of graphene-modified degradable materials
Note: the relative molecular masses of the degradable resins shown in table 3 are all about 20 ten thousand.
Degradability test
In the test of degradability of the materials, the materials of examples 1 to 3, 8, 10 and 13 (the material to be tested can be processed into a bar of 120mm in length by 15mm in height by 10mm in width by injection molding and machining) were tested for degradability using the following test methods, and the test results are shown in table 4.
Degradation test method:
step I): taking 2 sample bars, placing in a constant temperature drying oven, drying at 105 ℃ for 2 hours, weighing, and recording the initial mass as M0；
Step II): respectively placing the dried 2 sample strips in hard glass tubes with openings at one ends, respectively adding a proper amount of clear water to completely soak the sample strips, respectively placing the hard glass tubes into pressure water bath tanks using the clear water as a heat transfer medium, sealing, respectively filling nitrogen into the two pressure water bath tanks until the pressure reaches 2.0MPa, controlling the temperature inside the two pressure water bath tanks to be 170 ℃, and respectively marking the two pressure water bath tanks as S1 and S2;
step III): after 2 hours, taking out the sample strips in the S1, cleaning the sample strips with distilled water, putting the sample strips into a constant-temperature drying oven, drying the sample strips for 2 hours at 105 ℃, weighing the dried sample strips, and recording the residual mass as M1；
Step IV): after 15 days, the sample strips in the S2 are taken out, washed clean by distilled water, put into a constant-temperature drying oven, dried for 2 hours at 105 ℃, weighed, and the mass of the residual solid phase is recorded as M2；
Step V): calculating the degradation rate RdThe calculation formula is as follows:
RdS1＝(M0-M1)/M0×100％；
RdS2＝(M0-M2)/M0×100％。
the schematic structural diagram of the hard glass tube and the pressure water bath tank (mainly composed of a copper tube and a copper nut) in the step II) is shown in FIG. 1.
After 15 days in step IV), the mass measurement can be performed in the following manner for the case where the splines in S2 have substantially disappeared:
taking out the hard glass tube in S2, collecting supernatant to separate residual solid phase, cleaning the separated residual solid phase with distilled water, placing in a constant temperature drying oven, oven drying at 105 deg.C for 2 hr, weighing, and recording the mass of the residual solid phase as M2。
In the actual measurement process, in order to ensure the accuracy of measurement, the method can be repeated for a plurality of times, corresponding test results are recorded, and the average value of the test results can be obtained.
The results of the degradability tests for the materials of examples 1-3, 8, 10 and 13 are shown in table 4.
TABLE 4 degradability test results for the materials
Note: comparative example 1 in table 4 is a glycolic acid homopolymer of about 20 million relative molecular mass, without the graphene-modified glycolic acid polymer, and without any processing aids; the matrix in comparative example 2 was a glycolic acid homopolymer having a relative molecular mass of about 20 ten thousand, containing no graphene-modified glycolic acid polymer, but containing a processing aid, and the kind and content of the processing aid were the same as those in example 10.
As can be seen from the analysis of table 4, comparative example 1, which has a significantly changed shape due to too fast degradation rate under high temperature (e.g., 170 c), may prematurely lose its mechanical strength, and cannot be applied to a downhole environment at high temperature (e.g., about 170 c). The functionalized graphene is introduced into the material system, so that the thermal stability of the material under the high-temperature condition can be effectively improved, and the degradation rate of the material under the high-temperature condition can be significantly reduced to a certain extent, for example, the degradation rate of the example 10 material is about 21.6% within 2 hours at 170 ℃, under the condition of the degradation rate, the material can still keep the original basic shape, the mechanical strength of the material is maintained to a certain extent, and the phenomenon that the material rapidly collapses under the high-temperature condition can be effectively prevented.
Thermal stability test
The heat distortion temperatures of the materials of examples 1-3, 8, 10 and 13 were tested using a heat distortion temperature-Vicat softening point tester in accordance with GB/T1633-2000.
The test sample is a strip with a rectangular cross section, and the surface of the test sample is flat and smooth and has no defects such as air bubbles, saw cutting marks or cracks and the like. The dimensions of the material samples to be tested were: 120mm long, 15mm high and 10mm wide.
The heat transfer medium adopted in the test is methyl silicone oil, the temperature rise speed is controlled to be 120 ℃/h, the central distance between the two sample supports is 100mm, a vertical load is applied to the sample at the midpoint of the supports, the contact part of a pressure head of the load rod and the sample is semicircular, the radius of the contact part is (3 +/-0.2) mm, and the maximum bending normal stress of the loaded sample is 4.6kg/cm in the experimental process2。
The heat distortion temperature test results for the materials of examples 1-3, example 8, example 10, and example 13 are shown in table 5.
TABLE 5 Heat distortion temperature test results for materials
| Item | Heat distortion temperature (/ deg.C) |
| Example 1 | 178 |
| Example 2 | 183 |
| Example 3 | 189 |
| Example 8 | 194 |
| Example 10 | 203 |
| Example 13 | 185 |
| Comparative example 1 | 166 |
| Comparative example 2 | 172 |
Note: comparative example 1 in table 5 is a glycolic acid homopolymer of about 20 million relative molecular mass, without the graphene-modified glycolic acid polymer, and without any processing aids; the matrix in comparative example 2 was a glycolic acid homopolymer having a relative molecular mass of about 20 ten thousand, containing no graphene-modified glycolic acid polymer, but containing a processing aid, and the kind and content of the processing aid were the same as those in example 10.
As can be seen from the analysis of table 5, the heat distortion temperature of comparative example 1 is about 166 ℃, whereas the heat distortion temperature of the final material system can be effectively improved using a material prepared by compounding a graphene-modified glycolic acid polymer (having a low relative molecular mass, not greater than 10 ten thousand) with a degradable resin (e.g., a glycolic acid polymer having a high relative molecular mass, about 20 ten thousand), e.g., the heat distortion temperature of the material prepared in example 10 can be increased to about 203 ℃.
It can be seen that a member for a downhole tool (e.g., a bridge plug, fracturing ball or packer, etc.) made using the material of the present invention can be applied to high temperature downhole operations (e.g., temporary fracturing diverting fracturing operations) at a temperature of, for example, about 170 ℃. In contrast, comparative example 1 (i.e., a glycolic acid homopolymer having a relative molecular mass of about 20 million) had a heat distortion temperature of about 166 ℃ and, in the above-mentioned high-temperature environment, its mechanical properties were greatly reduced, whereby the plugging effect was lost, which was not favorable for the efficient performance of the temporary plugging diverting fracturing work, or even impossible.
Mechanical Property test
The materials of examples 1-3, 8, 10 and 13 were tested for tensile strength according to the method of GB/T1040.2-2006; the flexural strength of the materials of examples 1-3, 8, 10 and 13 was tested according to the GB/T9341-2008 method.
The test results of tensile strength and flexural strength of the materials of examples 1 to 3, example 8, example 10, and example 13 are shown in table 6.
TABLE 6 test results for tensile and flexural Strength of the materials
| Item | Tensile Strength (/ MPa) | Flexural Strength (/ MPa) |
| Example 1 | 112 | 202 |
| Example 2 | 126 | 213 |
| Example 3 | 145 | 192 |
| Example 8 | 164 | 247 |
| Example 10 | 178 | 268 |
| Example 13 | 152 | 229 |
| Comparative example 1 | 103 | 196 |
| Comparative example 2 | 109 | 205 |
Note: comparative example 1 in table 6 is a glycolic acid homopolymer of about 20 million relative molecular mass, without the graphene-modified glycolic acid polymer, and without any processing aids; the matrix in comparative example 2 was a glycolic acid homopolymer having a relative molecular mass of about 20 ten thousand, containing no graphene-modified glycolic acid polymer, but containing a processing aid, and the kind and content of the processing aid were the same as those in example 10.
As can be seen from the analysis in table 6, the tensile strength of the material system is significantly improved due to the introduction of the functionalized graphene, but the higher the amount of the functionalized graphene is, the better the material system is, because the higher the content of the functionalized graphene is, the higher the content of the functionalized graphene affects the toughness of the material, so that the material may be brittle to some extent. Therefore, the problem of the material system with reduced toughness due to the introduction of graphene can be improved by selecting a suitable and appropriate amount of other processing aids.
From the analysis, the functionalized graphene is introduced into the material disclosed by the invention, so that the thermal stability of a material system can be effectively improved, and the heat-resistant temperature of the material system is increased; in order to improve the dispersibility of graphene in the degradable resin, a glycolic acid polymer (which can be a glycolic acid homopolymer or a glycolic acid copolymer) is selected as an intermediate carrier of graphene, namely, the surface of graphene can be modified to obtain functionalized graphene, and then the functionalized graphene is uniformly pre-dispersed in the glycolic acid polymer by a chemical modification or physical blending method to obtain a graphene modified glycolic acid polymer, because the glycolic acid polymer and the degradable resin (with a hydrolytic functional group) generally have relatively good compatibility, a polymer continuous phase in the glycolic acid polymer (which is used as the intermediate carrier) compounded with the functionalized graphene can play a role of a 'compatibilizer', which is beneficial to uniformly dispersing the graphene in the final material and can effectively prevent the graphene from being dispersed in the final material with poor uniformity due to agglomeration, and adversely affects the mechanical properties and thermal stability of the final material.
The material of the present invention can be usually produced into a molded article by a molding method such as extrusion molding, injection molding, calender molding, blow molding, etc., or the molded article (sometimes referred to as "primary molded article") can be subjected to machining such as cutting, boring, cutting, etc. to produce a molded article (sometimes referred to as "secondary molded article") having a desired shape. Examples of the cutting process include turning, grinding, planing, and boring using a single-edge tool. As a cutting method using a variety of tools, there are milling, thread cutting, tooth cutting, carving, filing, and the like, and drilling may be included. As the cutting process, there are cutting with a cutter (saw), cutting with abrasive grains, cutting with heating and melting, and the like. In addition, special processing methods such as grinding and polishing, punching using a knife-like cutter, plastic working such as scribing, and laser processing, and the like can be applied.
It should be noted that the degradable material of the present invention can be used for manufacturing degradable packaging films, barrier films, mulching films, fibers, plates, sheets, bars or other shaped products besides being applied to downhole operations.
In the case where a solidified extruded polyglycolic acid resin molded product as a material for machining is melted by frictional heat during machining and a smooth surface is hard to appear, it is desirable to perform machining while cooling a cut surface or the like. Since the primary molded article may be deformed or colored if it excessively generates heat due to frictional heat generation, the primary molded article or the processed surface as a material for machining is preferably controlled to a temperature of 200 ℃ or less, preferably 150 ℃ or less.
The component for the downhole tool processed by the material can still maintain enough mechanical property under high temperature, can be used for temporary plugging and fracturing construction under high temperature and high humidity downhole environment conditions, can be easily removed after being degraded for a period of time under the downhole environment conditions according to actual application requirements, and cannot influence an underground reservoir stratum, so that the component is beneficial to improving the downhole construction efficiency and reducing the construction cost.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Furthermore, it should be understood that the various aspects recited, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (18)
1. A method of preparing a graphene-modified glycolic acid polymer, the method comprising the steps of: carrying out grafting reaction on the functionalized graphene and a glycolic acid polymer to obtain a graphene modified glycolic acid polymer; or
The method comprises the following steps: the functionalized graphene is physically blended with a glycolic acid polymer to obtain the graphene modified glycolic acid polymer.
2. The method as claimed in claim 1, wherein the grafting reaction is carried out by polymerizing the monomers for forming the glycolic acid polymer from 130-150 ℃, adding the functionalized graphene when the temperature is increased to 190-205 ℃ by using the gradient temperature rise I, and then increasing the temperature to 210-230 ℃ by using the gradient temperature rise II to obtain the graphene-modified glycolic acid polymer.
3. The preparation method according to claim 2, wherein the gradient temperature rise I is carried out by controlling the temperature rise rate to be 1-5 ℃/min, and carrying out the isothermal reaction for 1-2 hours at a temperature of 20 ℃ per rise; and the gradient temperature rise II is to control the temperature rise rate to be 1-2 ℃/min, and the temperature rises by 5 ℃ every time, so that the reaction is carried out for 1-2 hours at constant temperature.
4. The method of claim 2, wherein the amount of functionalized graphene charged is from 0.1 to 5 wt% of the theoretical mass of glycolic acid polymer calculated on the mass of monomers forming glycolic acid polymer; preferably 0.5-2 wt%.
5. The method of claim 1, wherein said glycolic acid polymer comprises glycolic acid homopolymer or/and glycolic acid copolymer.
6. The method of claim 1 wherein said glycolic acid polymer has a molecular weight of no more than 10 tens of thousands.
7. The method of any one of claims 1-6, wherein the functionalized graphene is obtained by:
(i) reacting the functional modifier with graphene oxide to obtain functionalized graphene oxide; the functional modifier is selected from isocyanate modifiers, silane coupling agents or organic amine modifiers;
(ii) and reducing the functionalized graphene oxide to obtain the functionalized graphene.
8. A graphene-modified glycolic acid polymer obtained by the production method according to any one of claims 1 to 7.
9. A graphene-modified degradable material, wherein a matrix resin in a raw material component of the degradable material comprises the degradable resin and the graphene-modified glycolic acid polymer according to claim 8.
10. The graphene-modified degradable material of claim 9, wherein the degradable material contains 2 to 50 wt% of graphene-modified glycolic acid polymer based on the total weight of the raw material components of the degradable material; preferably from 10 to 40 wt%; more preferably 15 to 30 wt%.
11. The graphene-modified degradable material of claim 9, wherein the degradable material comprises 50-100 wt% of a matrix resin, based on the total weight of the raw material components of the degradable material; preferably 60 wt% or more; more preferably 70 wt% or more.
12. The graphene-modified degradable material according to claim 9, wherein the degradable resin contained in the matrix resin has a hydrolyzable functional group selected from one or two or more of the following groups: ester, amide, hydroxyl, carboxyl, anhydride, and carbamate groups.
13. The graphene-modified degradable material according to claim 9, wherein the degradable resin has a molecular weight of not less than 10 ten thousand.
14. The graphene-modified degradable material of claim 12, wherein the degradable resin is selected from at least one of aliphatic polyester, polyhydroxy ester ether, polyhydroxy alkanoate, polyanhydride, polyamino acid, polyethylene oxide, polyphosphazene, polyether ester, polyesteramide, polyamide, sulfonated polyester, thermoplastic polyester elastomer or thermoplastic polyurethane elastomer, or any copolymer, mixture, derivative or combination thereof.
15. The graphene-modified degradable material of any one of claims 9 to 14, wherein the raw material components of the degradable material further comprise one or more than two of the following groups: compatilizer, flexibilizer, plasticizer, chain extender, hydrolysis regulation accelerant, hydrolysis regulation inhibitor, heat stabilizer, antioxidant, antibacterial agent and lubricant.
16. A method for preparing the graphene-modified degradable material according to any one of claims 9 to 15, wherein the method comprises the steps of: melt blending and extruding the degradable resin and the graphene modified glycolic acid polymer as defined in claim 8 to obtain the graphene modified degradable material as defined in any one of claims 9 to 15.
17. Use of the graphene modified degradable material of any one of claims 9 to 15 for processing to form a component for a downhole tool in an oil and gas field production operation.
18. Use of the graphene-modified degradable material according to any one of claims 9 to 15 for making degradable packaging films, barrier films, mulching films, fibers, plates, sheets, bars or other shaped articles.
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