CN112679923B - Degradable material suitable for hydrocarbon resource recovery and preparation method and application thereof - Google Patents
Degradable material suitable for hydrocarbon resource recovery and preparation method and application thereof Download PDFInfo
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- CN112679923B CN112679923B CN202011424345.1A CN202011424345A CN112679923B CN 112679923 B CN112679923 B CN 112679923B CN 202011424345 A CN202011424345 A CN 202011424345A CN 112679923 B CN112679923 B CN 112679923B
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- glycolic acid
- acid polymer
- grafted
- functional
- elastomer
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Images
Abstract
The invention relates to a degradable material suitable for hydrocarbon resource recovery, which comprises glycolic acid polymer and a functional elastomer component compounded with the glycolic acid polymer as raw materials; wherein the functional elastomer component comprises a thermoplastic elastomer, a grafted glycolic acid polymer compounded with the thermoplastic elastomer, and a functional stabilizer. The glycolic acid polymer is used as a base material, the functional elastomer component is used for modifying the glycolic acid polymer, the brittleness problem of the base material is improved, the material system has certain toughness, the grafted glycolic acid polymer is used as an active compatibilization component in the functional elastomer component, the glycolic acid polymer continuous phase is stably entangled and fused with the base material, the graft has an active functional group, and can form a strong chemical bond with the functional group on the molecular chain of the thermoplastic elastomer, so that the reduction of the interfacial tension between the base material and the thermoplastic elastomer is facilitated, and the excellent impact strength is endowed to the material system.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a degradable material suitable for hydrocarbon resource recovery and a preparation method and application thereof.
Background
As is well known, hydrocarbon resource recovery refers to the recovery of natural resources (e.g., natural gas, oil, etc.) remaining in a subterranean reservoir or subterranean zone by drilling into the subterranean reservoir while circulating a drilling fluid in a wellbore. In the actual exploration and development process of oil and gas fields, temporary plugging operation is needed to plug the current high-permeability production zone so as to implement process measures on other low-permeability production zones, after the process is completed, the temporary plugging is removed, a flow channel between the production zone and a shaft is established, and oil extraction and gas production of oil and gas wells are realized.
In performing temporary plugging operations, it is often necessary to use a downhole tool such as a bridge plug. At present, most of used bridge plugs are drillable or fishable, and after fracturing construction, the bridge plugs are usually required to be drilled, ground or fished so as to release a plugged oil layer; however, in the field construction, the drilling and grinding or fishing failure often occurs due to the deformation of the casing, and the drilling and grinding process requires high time and economic cost, and secondary pollution is caused to the underground reservoir because more liquid is used in the drilling and grinding process. Therefore, research and development of a degradable bridge plug with good safety are required.
At present, in the aspect of degradable bridge plugs, most of the degradable bridge plugs are made of degradable alloy materials, such as magnesium aluminum alloy and the like, although the degradable bridge plugs have good strength, the dissolution rate of the degradable bridge plugs is greatly influenced by the mineralization degree of well fluid, the degradable bridge plugs can reach a nominal dissolution effect only by being soaked in a cosolvent for a long time, and in the practical application process, the problems of midway setting, difficulty in later-stage plug drilling and the like can still occur for many times.
In order to solve the problems, various attempts have been made to partially or completely replace magnesium-aluminum alloy soluble metal materials with 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.
In response to this problem, there are cases where a degradable polymer material is combined with a non-degradable or non-soluble metal or resin to obtain a downhole tool having good thermal stability, but due to the presence of the non-degradable or non-soluble component, it remains in the well and is liable to cause production failure.
Therefore, there is a need to develop a degradable material with good thermal stability and still maintaining sufficient mechanical properties at high temperature, and the material can be processed into a downhole tool member for hydrocarbon resource recovery operation in high temperature downhole environment.
Disclosure of Invention
The invention aims to solve the problem that the existing degradable material is difficult to meet the requirements of high-depth underground drilling operation, and provides a degradable material suitable for hydrocarbon resource recovery.
Another object of the present invention is to provide a method for preparing the degradable material.
It is a further object of the present invention to provide uses of the degradable material.
The purpose of the invention is realized by the following technical scheme:
a degradable material suitable for hydrocarbon resource recovery comprises glycolic acid polymer and a functional elastomer component compounded with the glycolic acid polymer;
wherein the functional elastomer component comprises a thermoplastic elastomer, a grafted glycolic acid polymer compounded with the thermoplastic elastomer, and a functional stabilizer.
The degradable material of the invention takes glycollic acid polymer as a main base material, and adopts functional elastomer components to modify the glycollic acid polymer, so that the brittleness problem of the base material can be effectively improved, a material system has certain toughness, wherein, the functional elastomer component adopts grafted glycollic acid polymer as active compatibilization component, wherein the glycolic acid polymer continuous phase is stably entangled and fused with the substrate, and the graft grafted on the glycolic acid polymer has active functional groups, it can form stronger chemical bond with functional group on the molecular chain of the thermoplastic elastomer, is favorable for reducing the interfacial tension between the base material and the thermoplastic elastomer, ensures that the thermoplastic elastomer can be stably and uniformly dispersed in the base material, effectively solves the problem that partial thermoplastic elastomer is separated out from the base material due to poor compatibility of the two, and further endows the material system with excellent impact strength.
As a preferable technical scheme, the mass ratio of the glycolic acid polymer to the thermoplastic elastomer is 50-90: 50-10; the addition amount of the grafted glycolic acid polymer is 1-20wt% and the addition amount of the functional stabilizer is 0.1-5wt% based on the total mass of the glycolic acid polymer and the thermoplastic elastomer.
As a preferred technical solution, the thermoplastic elastomer is at least one selected from thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer.
The thermoplastic polyester elastomer is an elastomer mainly composed of a polyester block copolymer, and may be, for example, a block copolymer composed of a hard segment composed of a polyester and a soft segment composed of polyether, the hard segment may be selected from aromatic polyesters and aliphatic polyesters, specifically, from polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyhydroxyalkanoate, and the like, and the soft segment may be selected from polyether such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like; for example, the hard segment may be an aromatic polyester, specifically polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, or the like, and the soft segment may be an aliphatic polyester having a lower elastic modulus than that of the hard segment. The hard segment and the soft segment are selected mainly for obtaining desired degradation characteristics and mechanical characteristics, and therefore, the kinds of the hard segment and the soft segment or the ratio thereof may be adjusted. Further, since the thermoplastic polyester elastomer has an ester bond in its molecular chain structure, it has a characteristic of being easily disintegrated within a predetermined period of time. Further, the thermoplastic polyester elastomer may be selected from commercially available ones
P30B, P40B, P40H, P55B or
3046, 4047N and the like.
The thermoplastic polyurethane elastomer is a block copolymer obtained by condensing an isocyanate compound and a compound having a hydroxyl group, and may be at least one selected from a polyether type thermoplastic polyurethane elastomer or a polyester type thermoplastic polyurethane elastomer. The polyester type thermoplastic polyurethane elastomer having better hydrolytic properties can be selected in view of controlling degradability and disintegratability. Further, the thermoplastic polyurethane elastomer may be selected from commercially available ones
DP 1085A, DP 1485A or
1185A, 685A, WHT-1180, WHT-1185, and the like, available from Tantainan polyurethane corporation.
The thermoplastic polyamide elastomer is a block copolymer of a hard segment composed of polyamide and a soft segment composed of polyether and/or polyester, the hard segment may be selected from aliphatic polyamide, specifically from nylon 6, nylon 11, and nylon 12, and the soft segment may be selected from polyether such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. The hard segment and the soft segment are selected mainly for obtaining desired degradation characteristics and mechanical characteristics, and therefore, the kinds of the hard segment and the soft segment or the ratio thereof may be adjusted. Further, the thermoplastic polyamide elastomer may be selected from commercially available TPAE-10, TPAE-12, TPAE-23, and the like.
Preferably, the grafted glycolic acid polymer includes at least one of an acid anhydride-based grafted glycolic acid polymer and a glycidyl ester-based grafted glycolic acid polymer.
Further, the acid anhydride-based grafted glycolic acid polymer is preferably a maleic anhydride-grafted glycolic acid polymer, and the glycidyl ester-based grafted glycolic acid polymer is preferably a glycidyl methacrylate-grafted glycolic acid polymer.
In a preferred embodiment, the graft ratio of the above-mentioned glycolic acid polymer is 0.8 to 1.8%.
As a preferred solution, the relative molecular mass of the grafted glycolic acid polymer used in the functional elastomer component is not greater than the relative molecular mass of the ungrafted glycolic acid polymer.
Further, the relative molecular mass of the grafted glycolic acid polymer is not more than 10 ten thousand, for example, preferably 4 to 10 ten thousand, more preferably 5 to 8 ten thousand.
Further, the relative molecular mass of the ungrafted glycolic acid polymer is not less than 15 tens of thousands, for example, preferably 15 to 30 tens of thousands, more preferably 16 to 25 tens of thousands, and most preferably 18 to 22 tens of thousands.
As a preferred technical scheme, the functional stabilizer is functionalized graphene. The functionalized modified graphene has abundant active functional groups (for example, -NH) on the surface2or-NCO, etc.), these active functional groups can not only form stronger chemical bonds with the thermoplastic elastomer and glycolic acid polymer (such as terminal hydroxyl groups on the molecular chain), but also form stronger chemical bonds with the graft (such as epoxy functional groups on the molecular chain like glycidyl methacrylate) grafted to the glycolic acid polymer, so that the functionalized graphene can be stably combined in the composite of the "thermoplastic elastomer-grafted glycolic acid polymer" and dispersed into the base material of rigid degradable resin (such as glycolic acid polymer) by using the composite as an intermediate carrier, thereby enabling the graphene to be stably and uniformly dispersed in the final material system to improve the thermal stability of the final material system.
Further, the functionalized graphene 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 a preferred embodiment, the isocyanate modifier includes a diisocyanate, such as, but not limited to, one of commercially available hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, or dicyclohexylmethane diisocyanate; the silane coupling agents include gamma- (methacryloyloxy) propyltrimethoxysilane (such as, but not limited to, commercially available KH-570, A-174, Z-6030), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (such as, but not limited to, commercially available KH-560), gamma-aminopropyltriethoxysilane (such as, but not limited to, commercially available KH 550); the organic amine modifier includes an alicyclic amine such as, but not limited to, one of commercially available triethylenetetramine, 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.
Specific preparation steps of functionalized graphene will be exemplified in the detailed description.
According to the invention, the glycolic acid polymer comprises glycolic acid homopolymers and/or glycolic acid copolymers.
Further, the glycolic acid copolymer comprises at least one of a hydroxycarboxylic acid monomer repeating unit, a lactone monomer repeating unit, a carbonate monomer repeating unit, or an amide monomer repeating unit in addition to the glycolic acid repeating unit; wherein, is composed of- (-O-CH2The proportion of the glycolic acid repeating unit represented by-CO-) -is 50 wt% or more, preferably 70 wt% or more, more preferably 85 wt% or more, and still more preferably 90 wt% or more.
Further preferably, the other hydroxycarboxylic acid monomer is selected from at least one of lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid or 6-hydroxyhexanoic acid, the lactone monomer is selected from at least one of beta-propiolactone, beta-butyrolactone, gamma-butyrolactone or epsilon-caprolactone, the carbonate monomer is selected from trimethylene carbonate, and the amide monomer is selected from at least one of epsilon-caprolactam or gamma-butyrolactam.
The glycolic acid copolymer is most preferably a glycolic acid-lactic acid copolymer.
According to the invention, the grafted 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 is carried out at about 140 ℃ for about 2 hours, the temperature is raised to about 160 ℃ for about 2 hours, then the temperature is raised to about 190 ℃ for about 2 hours, the first dehydrating agent is added, the temperature is raised to about 200 ℃, the pressure is reduced to about-10 kPa gauge, the reaction is carried out for about 2 hours, the second dehydrating agent is added, the temperature is raised to about 205 ℃, the pressure is reduced to about-20 kPa gauge, the reaction is carried out for about 1 hour, then the temperature is raised to about 210 ℃, the pressure is reduced to about-50 kPa gauge, and the reaction is continued until the intrinsic viscosity of the system reaches about 0.5-0.6 dL/g.
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 contains 1g of monomer for preparing the glycolic acid polymer per 10-20mL, 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.
Preferably, 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.
In one embodiment of the present invention, the dehydrating agent may be selected from one of dicyclohexylcarbodiimide or dicyclopentylcarbodiimide, and the amount of the dehydrating agent used is 0.5 to 1.2% by mass of the monomer used for preparing the glycolic acid polymer.
Further, the dosage of the primary dehydrating agent is 50-70% of the total mass of the dehydrating agent, and the rest is the dosage of the secondary dehydrating agent.
And secondly, injecting an organic peroxide initiator and the graft into the system, continuing to react for about 10-30min, then raising the temperature to about 220 ℃, reducing the pressure to about-90 kPa gauge, and reacting for about 1 hour to sufficiently remove small molecular substances, thus obtaining the grafted glycolic acid polymer.
In one embodiment of the present invention, the organic peroxide initiator and the graft may be mixed uniformly in a mass ratio of 0.1-1:10, and then injected into the reaction system.
Further, the graft is used in an amount of 4 to 8% of the theoretical mass of the glycolic acid polymer obtained based on the mass of the monomers used for preparing the glycolic acid polymer.
Preferably, the organic peroxide initiator may be selected from dialkyl peroxides (such as, but not limited to, di-t-butyl peroxide, dicumyl peroxide, and the like), and the graft may be selected from anhydrides (e.g., maleic anhydride) or glycidyl esters (e.g., glycidyl methacrylate).
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, the temperature is maintained at about 220 ℃ for about 1 hour, the material is discharged and the resulting material is soaked with petroleum ether for a plurality of times to remove silicone oil on the surface, and dried (for example, but not limited to, vacuum drying).
The preparation method of the degradable material for recovering the hydrocarbon resources comprises the following steps:
step 1): firstly adding the thermoplastic elastomer, the grafted glycollic acid polymer and the functional stabilizer into a stirring kettle according to the dosage relation to carry out melt blending, thus obtaining a molten functional elastomer component;
step 2): adding the glycolic acid polymer into a double-screw extruder according to the dosage relationship, directly introducing the molten functional elastomer component prepared in the step 1) into a blending section of the double-screw extruder, blending the glycolic acid polymer with the molten functional elastomer component, and then extruding and granulating to obtain the degradable material.
Further, the temperature of the stirring kettle in the step 1) is controlled to be about 210 ℃ and 220 ℃, and the stirring speed is 40-100r/min, preferably 50 r/min.
Further, the temperature of the plasticizing section of the twin-screw extruder in the step 2) is controlled to be 200-.
As an embodiment, one or more than two processing aids including the following group may also be added as appropriate according to actual needs in the melt blending stage of step 2): plasticizers, chain extenders, hydrolysis control accelerators, hydrolysis control inhibitors, antioxidants, antimicrobials, lubricants, and the like to further improve the properties of the final material.
The degradable material can be processed into components for downhole tools, such as central tubes, upper and lower joints, rubber cylinders, fracturing balls and the like for bridge plugs, and can also be processed into products such as temporary plugging agent particles, temporary plugging agent fibers, temporary plugging balls and the like for exploitation operation of hydrocarbon resource recovery.
The degradable material of the invention can be applied to downhole operation and can be used for preparing degradable fibers, plates, sheets, bars or other shaped products.
Compared with the prior art, the invention has the following advantages:
1) the degradable material of the invention takes rigid degradable resin (such as glycolic acid polymer) as a main substrate, and adopts the functional elastomer component to modify the rigid degradable resin, so that the brittleness problem of the substrate can be effectively improved, the material system has certain toughness, and the grafted glycolic acid polymer is adopted as an active compatibilization component in the functional elastomer component, wherein the glycolic acid polymer continuous phase can be stably entangled and fused with the substrate, and the graft grafted onto the glycolic acid polymer has an active functional group (for example, if the graft is glycidyl methacrylate, the graft has an epoxy functional group), the graft can form a stronger chemical bond with a functional group (for example, a terminal hydroxyl group) on a thermoplastic elastomer molecular chain, which is beneficial to reducing the interfacial tension between the substrate and the thermoplastic elastomer, so that the thermoplastic elastomer can be stably and uniformly dispersed in the substrate, the problem that partial thermoplastic elastomer is separated out from the base material due to poor compatibility of the two can be effectively solved, and the material system is endowed with excellent impact strength;
2) the functional elastomer component adopted by the invention is also introduced with functionalized graphene, and the functionalized and modified graphene has abundant active functional groups (such as-NH) on the surface2or-NCO, etc.), these active functional groups can not only form stronger chemical bonds with the thermoplastic elastomer and glycolic acid polymer (such as terminal hydroxyl groups on the molecular chain), but also form stronger chemical bonds with the graft (such as epoxy functional groups on the molecular chain like glycidyl methacrylate) grafted to the glycolic acid polymer, so that the functionalized graphene can be stably combined in the composite of the "thermoplastic elastomer-grafted glycolic acid polymer" and dispersed into the base material of rigid degradable resin (such as glycolic acid polymer) by using the composite as an intermediate carrier, thereby enabling the graphene to be stably and uniformly dispersed in the final material system for improving the thermal stability of the final material system;
3) in the preparation method of the degradable material, the thermoplastic elastomer, the grafted glycollic acid polymer and the functional stabilizer are melted and blended, so that the branched active functional group in the grafted glycollic acid polymer is bonded with the terminal hydroxyl group in the thermoplastic elastomer to form stable chemical bond, thereby obtaining a melted and stable thermoplastic elastomer-grafted glycollic acid polymer compound, then the melted compound is directly introduced into the blending section of a double-screw extruder and is directly blended with a plasticized melted base material (namely the glycollic acid polymer which is not subjected to grafting modification), thereby avoiding the secondary thermal processing of the functional elastomer component, reducing the thermal degradation of the thermoplastic elastomer and the grafted glycollic acid polymer caused by repeated thermal processing, simplifying the working procedures, and in addition, due to the adoption of the grafted glycolic acid with smaller molecular weight for polymerization (relative to the glycolic acid polymer which is not subjected to graft modification), in the melt blending processing process, the graft glycolic acid copolymer is beneficial to properly reducing the acting force among macromolecular chains of the base material, plays a role similar to lubrication, can properly reduce the melt viscosity of a material system, and is convenient to improve the molding processability of the material system.
Drawings
Fig. 1 is a schematic structural diagram of a hard glass tube and a pressure water bath used in a degradability test.
Detailed Description
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.
In a high-temperature and high-humidity environment of high-depth underground drilling, an underground tool made of an existing degradable high polymer material is subjected to unexpected rapid degradation due to insufficient heat resistance of the underground tool, so that the mechanical property of the underground tool is remarkably reduced and the underground tool fails, non-degradable or non-soluble components are remained in a well to easily cause production faults, and the existing degradable material is difficult to be used for hydrocarbon resource recovery operation in the high-temperature underground environment.
In order to solve the problem, the invention provides a degradable material suitable for hydrocarbon resource recovery, and the raw materials of the degradable material comprise a glycollic acid polymer and a functional elastomer component compounded with the glycollic acid polymer; wherein the functional elastomer component comprises a thermoplastic elastomer, a grafted glycolic acid polymer compounded with the thermoplastic elastomer, and a functional stabilizer.
The degradable material of the invention takes the glycollic acid polymer as a main base material, and adopts the functional elastomer component to modify the glycollic acid polymer, thereby effectively improving the brittleness problem of the base material and leading the material system to have certain toughness, wherein, the functional elastomer component adopts grafted glycollic acid polymer as active compatibilization component, wherein the glycolic acid polymer continuous phase is stably entangled and fused with the substrate, and the graft grafted on the glycolic acid polymer has active functional groups, it can form stronger chemical bond with functional group on the thermoplastic elastomer, is favorable for reducing the interfacial tension between the base material and the thermoplastic elastomer, enables the thermoplastic elastomer to be stably and uniformly dispersed in the base material, effectively solves the problem that partial thermoplastic elastomer is separated out from the base material due to poor compatibility of the two, and further endows the material system with excellent impact strength.
Wherein the mass ratio of the glycolic acid polymer to the thermoplastic elastomer is 50-90: 50-10; the addition amount of the grafted glycolic acid polymer is 1-20wt% and the addition amount of the functional stabilizer is 0.1-5wt% based on the total mass of the glycolic acid polymer and the thermoplastic elastomer.
As a preferred technical solution, the thermoplastic elastomer is at least one selected from thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer.
Preferably, the glycolic acid polymer grafted by the graft comprises at least one of an acid anhydride-based graft glycolic acid polymer and a glycidyl ester-based graft glycolic acid polymer, and the graft ratio of the glycolic acid polymer grafted is 0.8 to 1.8%.
As a preferred solution, the relative molecular mass of the grafted glycolic acid polymer used in the functional elastomer component is not greater than the relative molecular mass of the ungrafted glycolic acid polymer.
Preferably, the functional stabilizer is functionalized graphene, the functionalized graphene is obtained by modifying the surface of graphene with a functional modifier, and the functional modifier is selected from any one of isocyanate modifiers, silane coupling agents or organic amine modifiers.
The technical scheme of the invention is further illustrated by the following specific examples, and the raw materials used in the invention are all commercial products unless otherwise specified.
Table 1 shows the specific compositions of the degradable materials of examples 1 to 9 and comparative examples 1 to 4; table 2-1 shows the weight average relative molecular mass of the starting materials, and Table 2-2 shows the type and graft ratio of the graft in the grafted glycolic acid polymer; table 3 shows the types of the thermoplastic elastomer and the functional stabilizer.
TABLE 1 raw material composition of degradable material and its parts by weight
TABLE 2-1 weight average relative molecular Mass of raw Material Components of degradable Material
The glycolic acid copolymer employed in example 5 of table 2-1 was a glycolic acid-lactic acid copolymer in which the proportion of glycolic acid repeat units was about 72 wt%; the glycolic acid copolymer used in example 7 was a glycolic acid-lactic acid copolymer in which the proportion of glycolic acid repeating units was about 80 wt%.
TABLE 2-2 types and graft ratios of grafts in the grafted glycolic acid polymers
| Item | Graft material | Graft ratio |
| Example 1 | Maleic anhydride | About 0.81% |
| Example 2 | Maleic anhydride | About 1.08% |
| Example 3 | Maleic anhydride | About 1.26% |
| Example 4 | Glycidyl methacrylate | About 1.34% |
| Example 5 | Glycidyl methacrylate | About 1.34% |
| Example 6 | Glycidyl methacrylate | About 1.78% |
| Example 7 | Glycidyl methacrylate | About 1.78% |
| Example 8 | Glycidyl methacrylate | About 1.65% |
| Example 9 | Glycidyl methacrylate | About 1.42% |
| Comparative example 1 | / | / |
| Comparative example 2 | / | / |
| Comparative example 3 | / | / |
| Comparative example 4 | Glycidyl methacrylate | About 1.78% |
The grafted glycolic acid polymer employed in table 2-2 can be a grafted glycolic acid homopolymer, exemplified herein for the preparation of glycidyl methacrylate grafted glycolic acid homopolymer, prepared as follows:
step i): adding a methyl silicone oil solution containing a dispersant MOA-3 into a stirring reactor, subsequently adding a glycolic acid monomer and stannous octoate, reacting for about 2 hours at about 140 ℃, heating to about 160 ℃ at a rate of 4 ℃/min for about 2 hours, heating to about 190 ℃ at a rate of 6 ℃/min for about 2 hours, adding a first dehydrating agent to the reactor, heating to about 200 ℃ at a rate of 2 ℃/min, reducing the pressure to about-10 kPa gauge, reacting for about 2 hours, adding a second dehydrating agent to the reactor, heating to about 205 ℃ at a rate of 1 ℃/min, reducing the pressure to about-20 kPa gauge, reacting for about 1 hour, then heating to about 210 ℃ at the speed of 1 ℃/min, decompressing to about-50 kPa gauge pressure, and continuing to react until the intrinsic viscosity of the system reaches about 0.5-0.6 dL/g;
step ii): when the intrinsic viscosity of the system reaches about 0.5-0.6dL/g, adding a mixture of di-tert-butyl peroxide and glycidyl methacrylate into the system, continuing to react for about 10-30min, then increasing the temperature to about 220 ℃ at the speed of 1 ℃/min, reducing the pressure to gauge pressure of about-90 kPa, and reacting for about 1 hour to fully remove small molecular substances;
step iii): after the reaction is finished, the absolute pressure is controlled to be less than 1kPa, the temperature is maintained at about 220 ℃ for about 1 hour, the material is discharged, the obtained material is soaked in petroleum ether for multiple times to remove the silicone oil on the surface, and the material is dried (such as but not limited to vacuum drying).
In step i), the dosage relationship of the related reaction raw materials, the catalyst and the dehydrating agent is as follows:
1g of glycolic acid monomer per 10-20mL of the methyl silicone oil solution (e.g., about 1g of glycolic acid monomer per 12mL of the methyl silicone oil solution in examples 4 and 5; about 1g of glycolic acid monomer per 10mL of the methyl silicone oil solution in examples 6 and 7 and comparative example 4; about 1g of glycolic acid monomer per 16mL of the methyl silicone oil solution in example 8; about 1g of glycolic acid monomer per 20mL of the methyl silicone oil solution in example 9);
the mass fraction of the dispersant MOA-3 in the methyl silicone oil solution was about 0.1 to 1% (e.g., about 0.4% in examples 4 and 5, about 0.6% in examples 6 and 7 and comparative example 4, about 1% in example 8, and about 0.1% in example 9);
stannous octoate was used in an amount of about 0.01-0.2% of the mass of glycolic acid monomer (e.g., about 0.08% in examples 4 and 5, about 0.1% in examples 6 and 7 and comparative example 4, about 0.18% in example 8, about 0.03% in example 9);
the amount of the dehydrating agent used was about 0.5 to 1.2% by mass of the glycolic acid monomer (for example, about 0.8% in examples 4 and 5, about 0.6% in examples 6 and 7 and comparative example 4, about 1.0% in example 8, about 1.2% in example 9), and the amount of the primary dehydrating agent was about 50 to 70% by mass of the total dehydrating agent (for example, about 55% in examples 4 and 5, about 65% in examples 6 and 7 and comparative example 4, about 70% in example 8, about 50% in example 9), and the remainder was the amount of the secondary dehydrating agent.
In step ii), the amount relationship of the relevant materials and the control time of the grafting reaction are as follows:
the mass ratio of glycidyl methacrylate to di-t-butyl peroxide is 10:0.1-1 (e.g., about 10:0.5 in examples 4 and 5, about 10:0.4 in examples 6 and 7 and comparative example 4, about 10:1 in example 8, about 10:0.1 in example 9), and the amount of glycidyl methacrylate added can be controlled to be about 4-8% of the theoretical mass of the resulting glycolic acid homopolymer calculated based on the mass of glycolic acid monomer (e.g., about 6% in examples 4 and 5, about 5% in examples 6 and 7 and comparative example 4, about 4% in example 8, about 8% in example 9);
after the mixture of di-t-butyl peroxide and glycidyl methacrylate was added to the system, the reaction was continued for about 10 to 30min (for example, the reaction was continued for about 20min in examples 4 and 5; the reaction was continued for about 17min in examples 6 and 7 and comparative example 4; the reaction was continued for about 12min in example 8; and the reaction was continued for about 28min in example 9).
The test method for the grafting ratio of glycidyl methacrylate grafted glycolic acid homopolymer is as follows:
(1) adding the prepared glycidyl methacrylate grafted glycolic acid homopolymer into hexafluoroisopropanol to be completely dissolved, then pouring into excessive ethanol (the volume ratio of the hexafluoroisopropanol to the ethanol is 1:15) to carry out precipitation, filtering and retaining precipitate;
(2) cleaning the precipitate with ethanol, and drying the precipitate in a vacuum drying oven at 85 deg.C for 24 hr to obtain purified glycidyl methacrylate grafted glycolic acid homopolymer;
(3) 1.0g of purified glycidyl methacrylate-grafted glycolic acid homopolymer was taken and added to 90mL of a mixed solution of hexafluoroisopropanol and xylene (the volume ratio of hexafluoroisopropanol to xylene was 1:4), 4mL of 0.1mol/L trichloroacetic acid (TCA) was added, and heated under reflux at 130 ℃ for 90min to complete the ring-opening reaction between the TCA and the epoxy group of glycidyl methacrylate, followed by addition of two drops of phenolphthalein indicator and titration measurement with 0.05mol/L KOH-ethanol standard solution.
For the preparation method of the maleic anhydride grafted glycolic acid homopolymer, reference is made to the above steps for preparing the glycidyl methacrylate grafted glycolic acid homopolymer, which are not described herein again, but the material selection, dosage relationship and relevant reaction conditions of the reaction system can be exemplified as follows:
in step i), the dosage relationship of the related reaction raw materials, the catalyst and the dehydrating agent is as follows:
tangle-solidup-1 g glycolic acid monomer per 10-20mL of methylsilicone oil solution (e.g., about 1g glycolic acid monomer per 20mL of methylsilicone oil solution in example 1; about 1g glycolic acid monomer per 18mL of methylsilicone oil solution in example 2; about 1g glycolic acid monomer per 14mL of methylsilicone oil solution in example 3);
the dispersant tangle-solidup is MOA-7, with a mass fraction in simethicone solution of about 0.1-1% (e.g., about 1% in example 1; about 0.8% in example 2, about 0.5% in example 3);
a catalyst is employed at a level of from about 0.01 to about 0.2% by mass of glycolic acid monomer (e.g., about 0.01% in example 1, about 0.06% in example 2, about 0.12% in example 3) using dibutyltin dilaurate;
the amount of a dehydrating agent is about 0.5 to 1.2% by mass of glycolic acid monomer (e.g., about 0.5% in example 1; about 0.8% in example 2; about 0.6% in example 3) and the amount of a primary dehydrating agent is about 50 to 70% by mass of the total dehydrating agent (e.g., about 50% in example 1; about 60% in example 2; about 70% in example 3), the remainder being the amount of a secondary dehydrating agent.
In step ii), the amount relationship of the relevant materials and the control time of the grafting reaction are as follows:
the organic peroxide initiator used is dicumyl peroxide, the mass ratio of maleic anhydride to dicumyl peroxide is 10:0.1-1 (e.g., about 10:0.6 in example 1; about 10:0.4 in example 2; about 10:0.1 in example 3), and the amount of maleic anhydride added can be controlled to be about 5% of the theoretical mass of glycolic acid homopolymer calculated based on the mass of glycolic acid monomer;
the reaction was continued for about 10-30min after adding the mixture of dicumyl peroxide and maleic anhydride to the system (e.g., about 15min for example 1; about 18min for example 2; about 24min for example 3).
The test method for the grafting yield of maleic anhydride grafted glycolic acid homopolymer is as follows:
(1) adding the prepared maleic anhydride grafted glycolic acid homopolymer into hexafluoroisopropanol to be completely dissolved, then pouring into excessive ethanol (the volume ratio of the hexafluoroisopropanol to the ethanol is 1:15) to carry out precipitation, filtering and retaining precipitate;
(2) washing the precipitate with ethanol, and drying the precipitate in a vacuum drying oven at 85 deg.C for 24 hr to obtain purified maleic anhydride grafted glycolic acid homopolymer;
(3) 0.5g of purified maleic anhydride grafted glycolic acid homopolymer is taken and added into 90mL of mixed solution of hexafluoroisopropanol and xylene (the volume ratio of the hexafluoroisopropanol to the xylene is 1:4), heated and refluxed until the mixture is completely dissolved, after the mixture is cooled to 90 ℃, a drop of distilled water and a drop of pyridine are added, then 1.5mL of 0.3mol/L KOH-ethanol standard solution is added, the mixture is heated and refluxed for 30min, cooled to 100 ℃, 6mL of isopropanol solution is rapidly added, two drops of phenolphthalein indicator are added, and the mixture is subjected to constant temperature titration measurement by using 0.01mol/L HCl-isopropanol standard solution under the magnetic stirring of a constant temperature water bath at 75 ℃.
TABLE 3 kinds of thermoplastic elastomer and functional stabilizer
The functional stabilizer in table 3 is functionalized graphene, and can be specifically prepared by the following steps:
preparation of graphene oxide
The Hummers method is used for preparing graphene oxide, and 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 excess oxidant, diluting with 140ml of distilled water, filtering while hot, and filteringWashing with 0.01mol/L HCl, absolute ethyl alcohol and deionized water until no SO is left 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.
② 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.
Preparing a degradable material:
the above examples 1-9 employ the following steps to prepare the degradable material:
step 1): firstly adding the thermoplastic elastomer, the grafted glycollic acid polymer and the functional stabilizer into a stirring kettle according to the dosage relation to carry out melt blending, thus obtaining a molten functional elastomer component;
step 2): adding the glycolic acid polymer into a double-screw extruder according to the dosage relationship, directly introducing the molten functional elastomer component prepared in the step 1) into a blending section of the double-screw extruder, blending the glycolic acid polymer with the molten functional elastomer component, and then extruding and granulating to obtain the degradable material.
The temperature of the stirring kettle in the step 1) is controlled to be about 210 ℃ and 220 ℃ (for example, about 220 ℃), and the rotating speed of stirring is 40-100r/min (for example, about 50 r/min).
The temperature of the plasticizing section of the double-screw extruder in the step 2) is controlled to be 200-210 ℃ (for example about 210 ℃), the temperature of the blending section is controlled to be 210-220 ℃ (for example about 220 ℃), and the temperature of the extrusion section is controlled to be 220-230 ℃ (for example about 230 ℃).
The materials of comparative examples 1-4 were prepared by melting and blending the raw material components in a twin screw extruder, followed by extrusion granulation. Wherein the temperature of the plasticizing section of the twin-screw extruder is controlled to be 200-210 ℃ (for example about 210 ℃), the temperature of the blending section is controlled to be 210-220 ℃ (for example about 220 ℃), and the temperature of the extrusion section is controlled to be 220-230 ℃ (for example about 230 ℃).
And (3) performance testing:
I. thermal weight loss test of material
The material was subjected to a thermogravimetric test (purge atmosphere: nitrogen 20 ml/min; crucible: Al 2500) using a thermal analyzer (model: NETZSCH STA 2500)2O3No cover is added; the heating rate is as follows: 5 c/min), the temperatures at which the materials prepared in examples 6 and 7 and comparative examples 1 to 4 were measured at a mass loss of 3% were selected, as shown in table 4.
TABLE 4 results of thermogravimetric testing of materials
| Item | Temperature (/ deg.C) corresponding to 3% mass loss |
| Example 6 | About 292.36 |
| Example 7 | About 284.62 |
| Comparative example 1 | About 265.89 |
| Comparative example 2 | About 228.56 |
| Comparative example 3 | About 243.27 |
| Comparative example 4 | About 257.91 |
Based on the test results in Table 4, it can be seen that, upon incorporation of a material consisting of only glycolic acid homopolymer (i.e., comparative example 1), either of thermoplastic elastomer (i.e., comparative example 2) and functional stabilizer (i.e., comparative example 3) or of thermoplastic elastomer and grafted glycolic acid polymer (i.e., comparative example 4), the initial decomposition temperature (i.e., temperature corresponding to 3% mass loss) of the resulting material was reduced compared to comparative example 1, while the initial decomposition temperature of the materials of examples 6 and 7 was significantly increased compared to comparative example 1, probably because the grafted glycolic acid polymer promoted the uniform and stable dispersion of the functional stabilizer (i.e., functionalized graphene) in the substrate, while the surface of the functional stabilizer had abundant active functional groups (e.g., -NH)2or-NCO, etc.) which can form stronger chemical bond between the grafted glycolic acid polymer and the thermoplastic elastomer, and can play a role in promoting the compatibility between the grafted glycolic acid polymer and the thermoplastic elastomer, so that the grafted glycolic acid polymer and the functional stabilizer have synergistic effect, and the high temperature resistance of the material system can be jointly improved.
Mechanical testing of materials
The materials obtained in examples 1 to 9 and comparative examples 1 to 4 were respectively subjected to tensile strength test according to the methods of GB/T1040.1 to 2018, and the tensile strength test was carried out on the material after being immersed in 20wt% hydrochloric acid (90 ℃ C.) for 12 hours.
Notched impact strength was measured according to GB/T1043.1-2008 for the materials obtained in examples 1-9 and comparative examples 1-4, respectively, and for the materials after immersion in 20wt% hydrochloric acid (90 ℃ C.) for 12 hours.
TABLE 5 mechanical Property test results of the materials
| Item | Tensile Strength (MPa) | Notched impact Strength (KJ/m)2) | Tensile Strength (MPa) after hydrochloric acid impregnation | Notched impact strength (KJ/m) after hydrochloric acid impregnation2) |
| Example 1 | About 105 | About 2.6 | About 64 | About 1.8 |
| Example 2 | About 108 | About 3.1 | About 69 | About 1.9 |
| Example 3 | About 112 | About 3.3 | About 76 | About 2.1 |
| Example 4 | About 118 | About 4.4 | About 83 | About 3.2 |
| Example 5 | About 113 | About 3.7 | About 77 | About 2.6 |
| Example 6 | About 134 | About 5.6 | About 103 | About 4.5 |
| Example 7 | About 129 | About 5.5 | About 96 | About 4.2 |
| Example 8 | About 125 | About 5.3 | About 97 | About 4.2 |
| Example 9 | About 121 | About 4.7 | About 91 | About 3.4 |
| Comparative example 1 | About 89 | About 1.3 | About 34 | About 0.6 |
| Comparative example 2 | About 83 | About 1.8 | About 26 | About 1.1 |
| Comparative example 3 | About 102 | About 2.3 | About 47 | About 1.3 |
| Comparative example 4 | About 97 | About 2.1 | About 58 | About 1.4 |
Based on the test results in table 5, it can be seen that the tensile strength and notched impact strength of the material system are significantly improved and the corrosion resistance of the material system is significantly improved by the inclusion of the functional elastomer component (consisting of the thermoplastic elastomer, the grafted glycolic acid polymer, and the functional stabilizer) in the material composition of example 6 compared to the material consisting of the glycolic acid homopolymer alone (i.e., comparative example 1), i.e., the tensile strength of the material of example 6 is reduced by about 23.1%, the notched impact strength is reduced by about 19.6%, and the tensile strength of the material of comparative example 1 is reduced by about 61.8%, and the notched impact strength is reduced by about 53.8% after immersion in hydrochloric acid solution under the same conditions.
The material component of comparative example 2 is a material in which a thermoplastic elastomer is directly introduced on the basis of a glycolic acid homopolymer, and although the tensile strength of the material system is reduced compared with that of comparative example 1, the notched impact strength of the material system is effectively improved, but the mechanical strength and the corrosion resistance of the material system are not improved well due to poor compatibility between the glycolic acid homopolymer and the thermoplastic elastomer.
The material component of comparative example 3 is to introduce the functional stabilizer on the basis of comparative example 2, so that the tensile strength and the notched impact strength are effectively improved compared with those of comparative example 2, but the dispersibility of the functional stabilizer in the base material resin (i.e. glycolic acid homopolymer) is still to be improved, so that the anti-corrosion improvement effect of the material system is poor.
The material component of comparative example 4 is based on comparative example 2 and is introduced with the grafted glycolic acid homopolymer, compared with comparative example 2, the tensile strength and the notch impact strength are improved to a certain extent, although the mechanical strength is not improved as compared with comparative example 3, the corrosion resistance of the material system is obviously better than that of comparative example 3.
Material degradability test
In the aspect of testing the degradability of the materials, the degradability of the degradable materials prepared in examples 1-9 and comparative examples 1-4 was tested by the following test methods, and the materials to be tested were processed into: specimens 120mm long by 15mm high by 10mm wide.
Degradability 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 one open end, 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 the pressure water bath tanks, 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 120 ℃, and respectively marking the two pressure water bath tanks as S1 and S2;
step III): after 2 days, the sample strips in the S1 are taken out, washed clean by distilled water, put into a constant-temperature drying oven, dried for 2 hours at 105 ℃, weighed, and the residual mass M is recorded1；
Step IV): after 10 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 residual mass M is recorded2；
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 10 days in step IV), the mass measurement can be performed in the following manner for the case where the sample strip in S2 has 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 of the degradable materials prepared in examples 1 to 9 and comparative examples 1 to 4 are shown in Table 6.
TABLE 6 degradability test results for the materials
The application of the material is as follows:
the material of the present invention can be processed into downhole tool components, such as base pipes for bridge packings, upper and lower joints, etc., for use in hydrocarbon resource recovery production operations.
In general, the material of the present invention can be molded into a molded article by a suitable 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 machined by cutting, boring, cutting, etc. to obtain 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.
The component for the downhole tool, which is processed by the material, can still keep enough mechanical performance under the high-temperature condition, can be used for operation (for example, temporary plugging and fracturing construction) under the high-temperature downhole environment condition, can be basically and completely degraded in the downhole environment for a period of time after the operation is finished, has no damage to an underground reservoir stratum, does not need drilling and grinding or fishing, can reduce the construction cost and improve the operation efficiency.
It is noted that the material of the present invention can be used to make degradable fibers, plates, sheets, rods or other shaped articles, in addition to downhole operations.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A degradable material suitable for hydrocarbon resource recovery is characterized in that the raw materials of the degradable material comprise a glycollic acid polymer and a functional elastomer component compounded with the glycollic acid polymer;
wherein the functional elastomer component comprises a thermoplastic elastomer, a grafted glycolic acid polymer compounded with the thermoplastic elastomer, and a functional stabilizer;
the grafted glycolic acid polymer comprises at least one of an anhydride-based grafted glycolic acid polymer or a glycidyl ester-based grafted glycolic acid polymer;
the functional stabilizer is functionalized graphene, the functionalized graphene is obtained by modifying the surface of graphene by using a functional modifier, and the functional modifier is selected from any one of isocyanate modifiers, silane coupling agents or organic amine modifiers.
2. The degradable material suitable for hydrocarbon resource recovery according to claim 1, wherein the mass ratio of the glycolic acid polymer to the thermoplastic elastomer is 50-90: 50-10;
the addition amount of the grafted glycolic acid polymer is 1-20wt% and the addition amount of the functional stabilizer is 0.1-5wt% based on the total mass of the glycolic acid polymer and the thermoplastic elastomer.
3. The degradable material suitable for hydrocarbon resource recovery of claim 1 wherein said thermoplastic elastomer is selected from at least one of thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer.
4. The degradable material suitable for hydrocarbon resource recovery according to claim 1, wherein said acid anhydride grafted glycolic acid polymer is preferably maleic anhydride grafted glycolic acid polymer, and said glycidyl ester grafted glycolic acid polymer is preferably glycidyl methacrylate grafted glycolic acid polymer.
5. The degradable material suitable for hydrocarbon resource recovery according to claim 1, wherein the graft ratio of the grafted glycolic acid polymer is 0.8-1.8%.
6. The degradable material suitable for hydrocarbon resource recovery of claim 1 wherein the relative molecular mass of the grafted glycolic acid polymer used in the functional elastomer component is not greater than the relative molecular mass of the ungrafted glycolic acid polymer.
7. The method for preparing a degradable material suitable for hydrocarbon resource recovery according to any one of claims 1 to 6, comprising the steps of:
step 1): firstly adding the thermoplastic elastomer, the grafted glycollic acid polymer and the functional stabilizer into a stirring kettle according to the dosage relation to carry out melt blending, thus obtaining a molten functional elastomer component;
step 2): adding the glycolic acid polymer into a double-screw extruder according to the dosage relationship, directly introducing the molten functional elastomer component prepared in the step 1) into a blending section of the double-screw extruder, blending the glycolic acid polymer with the molten functional elastomer component, and then extruding and granulating to obtain the degradable material.
8. Use of a degradable material according to any of claims 1 to 6 for hydrocarbon resource recovery, wherein said material is processed into downhole tool components or made into temporary plugging agent particles, temporary plugging agent fibers or temporary plugging balls for hydrocarbon resource recovery.
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