WO2024019035A1 - Composition de caoutchouc dégradable, élément en caoutchouc, élément d'étanchéité et procédé de production d'une composition de caoutchouc dégradable - Google Patents

Composition de caoutchouc dégradable, élément en caoutchouc, élément d'étanchéité et procédé de production d'une composition de caoutchouc dégradable Download PDF

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Publication number
WO2024019035A1
WO2024019035A1 PCT/JP2023/026218 JP2023026218W WO2024019035A1 WO 2024019035 A1 WO2024019035 A1 WO 2024019035A1 JP 2023026218 W JP2023026218 W JP 2023026218W WO 2024019035 A1 WO2024019035 A1 WO 2024019035A1
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Prior art keywords
rubber
degradable
hydrolysis
mass
water
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PCT/JP2023/026218
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English (en)
Japanese (ja)
Inventor
樹来 小林
和洋 高原
卓磨 小林
康志 海老原
壮慶 東瀬
京介 久保田
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興国インテック株式会社
株式会社クレハ
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Publication of WO2024019035A1 publication Critical patent/WO2024019035A1/fr

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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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/12—Packers; Plugs
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells

Definitions

  • the present invention relates to a degradable rubber composition, a rubber member, a sealing member, and a method for producing a degradable rubber composition, and particularly to a degradable rubber composition, a rubber member, and a sealant that naturally disintegrate after a predetermined period of time.
  • the present invention relates to a member and a method for producing a degradable rubber composition.
  • FIG. 6 is an explanatory diagram showing an overview of the hydraulic fracturing method.
  • the underground layer 50 is excavated from the well 10 on the ground surface 11 using a drill or the like, and reaches the mining layer 51 where hydrocarbon resources confined underground, for example, several thousand meters deep, are distributed.
  • An excavated hole 13 is formed.
  • fluid such as water at high pressure into the formed excavation hole 13
  • the rock of the mining layer 51 is crushed and cracks 15 are generated in the rock of the mining layer 51. Hydrocarbon resources trapped in the mining layer 51 are released from the cracks 15 generated in this way (see, for example, Patent Document 1).
  • the drill hole 13 is sealed at one or more locations with a sealing member 100 such as a frac plug, and a part of the drill hole 13 is sealed. It is necessary to form a space sealed by the sealing member 100. At this time, the sealing member 100 needs to have a function of suppressing fluid from flowing out from the space.
  • a sealing member 100 that is decomposed by being exposed to an environment in which a fluid such as water is present in the borehole 13 for a predetermined period of time is used.
  • a sealing member 100 one is known that is composed of a resin member made of a degradable resin such as polylactic acid and a rubber member made of a degradable rubber component.
  • the degradable rubber component used as the rubber member of the sealing member 100 is exposed to an environment where a fluid such as water is present for a predetermined period of time and hydrolysis progresses, the degradable rubber component remains in a gel-like or clay-like state. A state of high viscosity is maintained. Specifically, even if the hardness of conventional degradable rubber components reaches zero, they will not break into small pieces unless external force is applied to them. That is, in the conventional sealing member 100, the rubber member maintains its shape and remains in the excavated hole 13 without collapsing.
  • the sealing member 100 In order to remove the remaining sealing member 100 from the excavated hole 13, stress is removed from the outside of the sealing member 100 by inserting a drill or the like into the excavation hole 13 and crushing the sealing member 100 with the drill or the like. It is necessary to add and break it into small pieces. Therefore, due to its high viscosity, it may stick to the tip of the drill and obstruct the work, and may interfere with the separation work of the liquid after recovery. From the above, the sealing member 100 has the sealing performance as a rubber member, and after being continuously exposed to a fluid such as water for a predetermined period of time, it can be easily broken into small pieces without applying stress from the outside. There is a need for a rubber member that can be removed.
  • the present invention has been made in view of the above circumstances, and has the sealing performance of a rubber member as a sealing member, and does not apply stress from the outside after being continuously exposed to a fluid such as water for a predetermined period of time.
  • An exemplary object of the present invention is to provide a degradable rubber composition, a rubber member, a sealing member, and a method for producing a degradable rubber composition that can be easily removed by breaking it into small pieces.
  • the present invention has the following configuration.
  • a sealing member comprising at least a portion of the rubber member described in (2) above.
  • a decomposable rubber component comprising a kneading step of kneading raw materials containing an acidic hydrolysis accelerator to promote the degradable rubber component, wherein the acidic hydrolysis accelerator is contained in an amount of 40 parts by mass or more based on 100 parts by mass of the degradable rubber component.
  • the sealing member has the sealing performance as a rubber member, and after being continuously exposed to a fluid such as water for a predetermined period of time, it can be easily broken into small pieces without applying stress from the outside.
  • a removable degradable rubber composition, a rubber member, a sealing member, and a method for producing a degradable rubber composition can be provided.
  • Embodiment 1 The degradable rubber composition (hereinafter sometimes simply referred to as “degradable rubber composition”) according to Embodiment 1 will be described below.
  • the degradable rubber composition contains a degradable rubber component and a hydrolysis accelerator, and is suitably used as a material for a rubber member constituting a sealing member used, for example, in a hydraulic fracturing method.
  • a rubber member formed using a degradable rubber composition has sealing performance as a rubber member of a sealing member.
  • a rubber member formed using a degradable rubber composition has the characteristic that after being continuously exposed to a fluid such as water for a predetermined period of time, it breaks into pieces without applying stress from the outside. Specifically, when the hardness of the degradable rubber component of this embodiment reaches 0, it breaks down into small pieces (natural disintegration described below) without applying any external force.
  • predetermined time means the time it takes for the rubber member to naturally disintegrate due to the progress of hydrolysis when the rubber member starts being exposed to a fluid such as water and continues to be exposed thereafter. .
  • the time required for the rubber member to naturally disintegrate means that when the rubber member begins to be exposed to a fluid such as water and continues to be exposed to it, hydrolysis progresses and the rubber member naturally disintegrates. It means the time until it collapses.
  • the rubber member when a rubber member "naturally disintegrates", it means that the rubber member is unable to maintain its shape and collapses into small pieces after being exposed to a fluid such as water for a predetermined period of time. means. If the temperature conditions differ, the "predetermined time” may also change, so the performance as a rubber member needs to be evaluated under constant conditions.
  • the time (predetermined time) until the rubber member spontaneously disintegrates is evaluated under a certain condition that the rubber member is continuously exposed to water at 93°C.
  • the time it takes for the surface hardness (HsA) of a rubber member composed of hydrolyzable rubber molecules to reach 0 (zero) is a predetermined number of days (for example, 7 days) when exposed to water at 93°C.
  • the degradable rubber component includes a millable rubber material.
  • millable rubber material means a kneaded type rubber material, that is, a rubber material that can be kneaded.
  • a kneaded type rubber material is a rubber material that is solid at room temperature before vulcanization, and is distinguished from a liquid injection type rubber material. Since millable rubber materials are solid at room temperature, they are suitable for kneading using kneaders, rollers, etc. Even if a large amount of powdered additives are added, the additives will not be absorbed within the millable rubber material by kneading. Can be uniformly dispersed.
  • liquid-pouring rubber materials they are liquid at room temperature, so if a large amount of powdered additives are added, the solubility limit may be reached, phase separation may occur, or the additives may become lumps. It may be difficult to disperse the material evenly.
  • millable rubber materials include materials containing at least one member selected from the group consisting of urethane rubber, natural rubber, isoprene rubber, ethylene propylene rubber, butyl rubber, styrene rubber, acrylic rubber, aliphatic polyester rubber, and chloroprene rubber. Can be done.
  • thermoplastic elastomers such as polyester thermoplastic elastomers and polyamide thermoplastic elastomers, which are materials having properties similar to those of millable rubber materials, can also be included in the concept of millable rubber materials.
  • Millable rubber materials are composed of hydrolyzable rubber molecules.
  • the hydrolyzable rubber molecule is preferably a rubber molecule having a hydrolyzable functional group in the main chain of the rubber molecule.
  • the rubber molecule may have a hydrolyzable functional group not only in the main chain but also in the crosslinked portion. Examples of hydrolyzable functional groups include urethane groups, ester groups, amide groups, carboxyl groups, hydroxyl groups, and silyl groups.
  • the hydrolyzable functional group may be present in some or all of the repeating units constituting the rubber molecule.
  • the mass average molecular weight of the rubber molecules constituting the millable rubber material is, for example, 10,000 or more.
  • the mass average molecular weight is 10,000 or more, handling and workability as a millable rubber tends to be good.
  • the mass average molecular weight of the rubber molecules constituting the millable rubber material can be adjusted according to the content ratio of the hydrolysis accelerator and hydrolysis inhibitor, which will be described later, so that the rubber member will naturally maintain its properties after being exposed to fluids such as water. You can control the time it takes to collapse.
  • urethane rubber is preferable from the viewpoint of controlling sealing performance such as hardness and elasticity as a rubber member, and controlling decomposition performance and disintegration performance.
  • Urethane rubbers include ester-type urethane rubbers, ether-type urethane rubbers, etc., and ester-type urethane rubbers having a hydrolyzable functional group are particularly preferred.
  • urethane rubber includes thermoplastic type, liquid injection type, etc.
  • the hydrolysis accelerator described later is a powder, it is necessary to use a predetermined amount or more of the hydrolysis accelerator.
  • Millable type urethane rubber is preferable in order to incorporate it into the degradable rubber composition.
  • the degradable rubber component preferably contains a millable rubber material as a main component.
  • the degradable rubber component may contain rubber materials other than the millable rubber material as long as the properties of the millable rubber material used in this embodiment are not affected.
  • the hydrolysis accelerator is a powder that becomes acidic or basic when it comes into contact with water, and is a component that promotes hydrolysis of the rubber molecules of the degradable rubber component.
  • "powder” means a substance that is powder or particulate at room temperature and in a state not in contact with water (dry state), and the particle size is 200 ⁇ m or less.
  • This acidic or basic aqueous solution promotes hydrolysis of rubber molecules.
  • a powder that exhibits acidity when in contact with water and that promotes hydrolysis of rubber molecules of a degradable rubber component when in contact with water is referred to as an acidic hydrolysis promoter.
  • a powder that exhibits basicity upon contact with water and that promotes hydrolysis of rubber molecules of a degradable rubber component upon contact with water is referred to as a basic hydrolysis promoter.
  • the acidic hydrolysis accelerator examples include mineral powders such as silica, clay, talc, aluminum sulfate, barium sulfate, calcium sulfate, and alumina colloid. Note that the acidic hydrolysis accelerator is not limited to mineral powder. As the acidic hydrolysis accelerator, these substances may be used alone, or a plurality of substances may be used in combination.
  • the content of the acidic hydrolysis accelerator is 10 parts by mass or more, preferably 20 parts by mass or more, and 40 parts by mass or more, based on 100 parts by mass of the degradable rubber component. More preferably, the amount is 40 parts by mass, particularly preferably 40 parts by mass.
  • the content of the acidic hydrolysis accelerator is 10 parts by mass or more, the decomposition of the degradable rubber component is promoted, and the decomposed substance (hereinafter referred to as decomposed product) becomes clay-like, and the clay-like shape is maintained.
  • the content of the acidic hydrolysis accelerator is 20 parts by mass or more, the decomposed product collapses due to external force.
  • the decomposed product naturally disintegrates without applying external force.
  • the content of the acidic hydrolysis accelerator in the degradable rubber composition is 40 parts by mass or more based on 100 parts by mass of the degradable rubber component, the rubber can be continuously exposed to a fluid such as water for a predetermined period of time. It is possible to obtain a degradable rubber composition constituting a sealing member whose molecules suitably disintegrate naturally and which can be easily removed by breaking into small pieces without applying external stress.
  • the hydrolysis promoter contains an acidic hydrolysis promoter, and may further contain a basic hydrolysis promoter to the extent that the effect of the acidic hydrolysis promoter is not impaired.
  • Examples of the basic hydrolysis promoter include basic oxides such as metal oxide particles, salts of weak acids and strong bases, and metal hydroxides.
  • Examples of the basic oxide include magnesium oxide, potassium oxide, and calcium oxide.
  • Examples of the salts of weak acids and strong bases include sodium carbonate, sodium hydrogencarbonate, and calcium carbonate.
  • Examples of the metal hydroxide include sodium hydroxide and potassium hydroxide. Note that the basic hydrolysis promoter is not limited to the above-mentioned basic oxides, salts of weak acids and strong bases, or metal hydroxides.
  • As the basic hydrolysis accelerator these substances may be used alone, or a plurality of substances may be used in combination.
  • the content of the basic hydrolysis accelerator is 1 part by mass or more based on 100 parts by mass of the degradable rubber component.
  • the degradable rubber composition may further contain a hydrolysis inhibitor in addition to the degradable rubber component and the hydrolysis promoter.
  • the hydrolysis inhibitor is a component that inhibits the hydrolysis of rubber molecules promoted by the hydrolysis promoter.
  • As the hydrolysis inhibitor for example, a component that reacts with the carboxylic acid at the end of the carboxyl group produced by hydrolysis of rubber molecules and inhibits the chain reaction of the hydrolysis reaction can be used.
  • hydrolysis inhibitor examples include polymeric carbodiimide compounds.
  • these substances may be used alone, or a plurality of substances may be used in combination.
  • the properties of the hydrolysis inhibitor are not particularly limited, but for example, powder can be used. By using the millable rubber material, the powder hydrolysis inhibitor can be kneaded well.
  • the content of the hydrolysis inhibitor is preferably 1 part by mass or more based on 100 parts by mass of the degradable rubber component.
  • the degradable rubber composition may contain, for example, a reinforcing agent, etc., as appropriate, in addition to the above-mentioned constituent components.
  • a reinforcing agent is added for the purpose of improving the strength of a rubber member when the degradable rubber composition is used as a sealing member.
  • reinforcing agents include silica and carbon black.
  • the mineral powder when a mineral powder such as silica is used as an acidic hydrolysis accelerator, the mineral powder may function both as an acidic hydrolysis accelerator and as a reinforcing agent. can.
  • the acidic hydrolysis promoter include mineral powders such as silica, clay, talc, aluminum sulfate, barium sulfate, calcium sulfate, and alumina colloid.
  • the method for producing the degradable rubber composition is not particularly limited, and general production methods can be employed. That is, the degradable rubber composition can be produced by a manufacturing method including, for example, a kneading step of kneading raw materials containing at least a degradable rubber component and an acidic hydrolysis accelerator, and a vulcanization step of crosslinking the kneaded raw materials. can be manufactured.
  • the kneading method for kneading the raw materials in the kneading step is not particularly limited, and can be performed by methods such as open rolls, pressure kneaders, and Banbury mixers.
  • a degradable rubber member can be produced by putting a degradable rubber composition into a predetermined mold and vulcanizing it under predetermined vulcanization conditions.
  • the vulcanization conditions for vulcanizing the degradable rubber composition can be, for example, a temperature in the range of 120°C to 200°C and a time of about 5 to 60 minutes.
  • the temperature is less than 120°C, the decomposition of the crosslinking agent does not proceed and the crosslinking reaction of the rubber does not occur.
  • the temperature exceeds 200° C., the compound (high molecular compound (polymer)) deteriorates.
  • the temperature is in the range of 120°C to 200°C, crosslinking of the rubber occurs and no deterioration of the polymer occurs.
  • the time range As the vulcanizing agent, sulfur, organic peroxide, etc. can be used. Examples of the organic peroxide include peroxyketal, dialkyl peroxide, diacyl peroxide, and peroxy ester.
  • the hydraulic fracturing method which is one example in which the sealing member of this embodiment is used, is the same as the method described with reference to FIG. 6, and the description thereof will be omitted with reference to FIG.
  • the sealing member of this embodiment is formed using the degradable rubber composition according to this embodiment, and the material of the rubber member is different from that of the conventional sealing member 100. different.
  • FIG. 1 is a schematic diagram showing a sealing member formed using a degradable rubber composition according to Embodiment 1.
  • the sealing member 1 includes a main body 2 having a substantially cylindrical shape extending in the longitudinal direction L, and a sealing member 1 disposed on both ends of the main body 2 in the longitudinal direction L so as to be slidable in the longitudinal direction L.
  • the rubber member 3 includes a pair of sleeves 4 and a rubber member 3 disposed between the pair of sleeves 4.
  • FIG. 1(a) is a schematic diagram showing a state in which the pair of sleeves 4 are in a predetermined position and the rubber member 3 is not compressed.
  • FIG. 1(a) is a schematic diagram showing a state in which the pair of sleeves 4 are in a predetermined position and the rubber member 3 is not compressed.
  • FIG. 1(b) is a schematic diagram showing a state in which the pair of sleeves 4 are moved toward the center in the longitudinal direction L (toward the rubber member 3), and the rubber member 3 is compressed.
  • the "longitudinal direction L" is the direction in which the substantially cylindrical tube of the sealing member 1 extends, the direction in which the central axis extends, and the direction in which the sealing member 1 moves in the excavated hole 13. be.
  • both end sides in the longitudinal direction L means the front end side and the rear end side when the sealing member 1 moves within the excavated hole 13.
  • the rubber member 3 is a member formed from the degradable rubber composition according to the first embodiment. As described above, the rubber member 3 is a tubular member that is disposed between the pair of sleeves 4 and covers the periphery of the main body 2. As shown in FIG. 1(b), the rubber member 3 is deformed by being compressed by the pair of sleeves 4, and expands in a direction substantially perpendicular to the longitudinal direction. As a result, the sealing member 1 has a larger diameter (a diameter substantially perpendicular to the longitudinal direction) at the rubber member 3 portion. As the rubber member 3 expands in this manner, the rubber member 3 and the wall surface of the excavated hole 13 come into close contact with each other, making it possible to seal the excavated hole 13.
  • the rubber member 3 is formed from the degradable rubber composition according to the present embodiment, and the degradable rubber composition constituting the rubber member 3 of the sealing member 1 has a sealing function and a predetermined After a period of time, it has the ability to break into small pieces without applying external stress.
  • the parts of the sealing member 1 other than the rubber member 3, that is, the main body 2 and the pair of sleeves 4, may be formed from a degradable rubber composition or from other degradable materials. It may be something that is done. Examples of such degradable materials include polyglycolic acid (PGA) and polylactic acid (PLA).
  • the portions of the sealing member 1 other than the rubber member 3 be decomposed in approximately the same time as the decomposition time of the degradable rubber composition.
  • the degradable rubber composition of this embodiment is not limited to the above-mentioned hydraulic fracturing method, and may be used in other methods that require sealing performance, decomposition performance, and disintegration performance.
  • Example 1 100 parts by mass of polyester-based millable urethane rubber as a degradable rubber component and 40 parts by mass of silica as an acidic hydrolysis accelerator and reinforcing agent were used as raw materials.
  • the degradable rubber component was kneaded using an open roll, a hydrolysis accelerator was added as an additive, and the mixture was further kneaded to obtain the degradable rubber composition of Example 1.
  • the obtained decomposable rubber composition was placed in a mold and vulcanized by heating under pressure at 120 to 200°C for 5 to 60 minutes.
  • An organic peroxide was used as a vulcanizing agent. In this way, a cube-shaped rubber sample with one side of 20 mm was produced. A plurality of rubber samples were produced corresponding to each immersion time described below.
  • FIG. 2 shows the measurement results of surface hardness.
  • FIG. 2 is a graph showing the results of measuring the surface hardness of the rubber samples of Example 1 and Comparative Examples 1 and 2.
  • the vertical axis shows the surface hardness (HsA)
  • the horizontal axis shows the immersion time (days).
  • the measurement results of Example 1 are indicated by " ⁇ " (black circles) in FIG. It can be seen that the surface hardness (HsA) of the rubber sample of Example 1 became 0 (zero) 7 days after the start of immersion.
  • FIG. 3 is a schematic diagram showing the state before and after the rubber sample of Example 1 spontaneously disintegrates.
  • FIG. 3(a) is a schematic diagram showing a state immediately after the rubber sample 30 is produced. At this point, the rubber sample 30 maintains a cubic shape of 20 mm on one side, and the decomposition of the degradable rubber component has not progressed. Note that this state before immersion is the same not only in Example 1 but also in other Examples and Comparative Examples.
  • FIG. 3(b) shows the rubber sample 30 shown in FIG. 3(a) placed in a glass bottle 34 containing ion-exchanged water 36, and shows the state after the rubber sample 30 spontaneously disintegrated seven days after immersion was started.
  • FIG. 3(b) shows that small pieces 32 of the naturally disintegrated rubber sample 30 are precipitated in the ion-exchanged water 36 at the bottom of the glass bottle 34.
  • the small pieces 32 of the naturally disintegrated rubber sample 30 shown in FIG. 3(b) are broken down into small pieces of, for example, 1 mm or less, and are powdered when taken out from the glass bottle 34. From these results, it can be seen that the rubber sample 30 of Example 1 spontaneously disintegrated 7 days after the start of immersion.
  • Comparative example 1 A rubber sample was prepared in the same manner as in Example 1, except that the content ratio of the hydrolysis accelerator was 20 parts by mass based on 100 parts by mass of the degradable rubber component, and the surface hardness (HsA) was measured. The measurement results of Comparative Example 1 are indicated by " ⁇ " (open squares) in FIG. It can be seen that the surface hardness (HsA) of the rubber sample of Comparative Example 1 became 0 (zero) 7 days after the start of immersion.
  • FIG. 4 is a schematic diagram showing the state of the rubber samples of Comparative Examples 1 and 2 after they are decomposed.
  • FIG. 4(a) shows the rubber sample 300 of Comparative Example 1 put into a glass bottle 34 containing ion-exchanged water 36, and after the rubber sample 300 of Comparative Example 1 has decomposed, that is, 7 days after starting immersion.
  • 3 is a schematic diagram showing the appearance of a rubber sample 300 of Comparative Example 1.
  • FIG. FIG. 4A shows that although the rubber sample 300 is decomposed, it does not spontaneously disintegrate, and maintains a cubic shape similar to the state immediately after the rubber sample 300 of Comparative Example 1 was produced. This point differs from FIG. 3(b), which shows the state after the rubber sample 30 spontaneously disintegrates in Example 1.
  • Rubber sample 300 of Comparative Example 1 had a surface hardness (HsA) of 0 (zero) (decomposed) after 7 days from the start of immersion, but had a clay-like high viscosity and a cubic shape. was maintained. That is, rubber sample 300 of Comparative Example 1 did not disintegrate spontaneously.
  • HsA surface hardness
  • Comparative example 2 A rubber sample was prepared in the same manner as in Example 1, except that the content ratio of the hydrolysis accelerator was 30 parts by mass based on 100 parts by mass of the degradable rubber component, and the surface hardness (HsA) was measured. The measurement results of Comparative Example 2 are indicated by " ⁇ " (open triangle) in FIG. It can be seen that the surface hardness (HsA) of the rubber sample of Comparative Example 2 became 0 (zero) 7 days after the start of immersion.
  • FIG. 4(b) shows the rubber sample 310 of Comparative Example 2 put into a glass bottle 34 containing ion-exchanged water 36, and after the rubber sample 310 of Comparative Example 2 has decomposed, that is, 7 days after starting immersion.
  • 3 is a schematic diagram showing the state of a rubber sample 310 of Comparative Example 2.
  • FIG. 4(b) the rubber sample 310 has decomposed but has not spontaneously disintegrated. Seven days after the start of immersion, the rubber sample 310 of Comparative Example 2 is poked with a stick, that is, by applying an external force. It shows a state where the shape has been destroyed.
  • Rubber sample 310 of Comparative Example 2 had a surface hardness (HsA) of 0 (decomposed) 7 days after the start of immersion, but had a clay-like high viscosity. That is, rubber sample 310 of Comparative Example 2 did not disintegrate spontaneously. By applying stress from the outside to the rubber sample 310 of Comparative Example 2, the shape collapsed.
  • HsA surface hardness
  • Example 2 A rubber sample was prepared in the same manner as in Example 1, and the surface hardness (HsA) was measured. The measurement results are shown in FIG. FIG. 5 is a graph showing the results of measuring the surface hardness of the rubber samples of Examples 2 to 4. The measurement results of Example 2 are indicated by " ⁇ " (black circles) in FIG. It can be seen that the surface hardness (HsA) of the rubber sample of Example 2 became 0 (zero) 7 days after the start of immersion, as in Example 1. Similarly to Example 1, the rubber sample of Example 2 had spontaneously disintegrated 7 days after the start of immersion.
  • Example 3 A rubber sample was prepared in the same manner as in Example 1, except that 3 parts by mass of a polymeric carbodiimide compound as a hydrolysis inhibitor was added to 100 parts by mass of the degradable rubber component, and the surface hardness (HsA) was measured.
  • the measurement results of Example 3 are indicated by " ⁇ " (black triangle) in FIG. It can be seen that the surface hardness (HsA) of the rubber sample of Example 3 became 0 (zero) 9 days after the start of immersion.
  • the rubber sample of Example 3 had spontaneously disintegrated as in Example 1 9 days after the start of immersion. This shows that the addition of the hydrolysis inhibitor suppressed the hydrolysis of the degradable rubber component. From the graph in FIG.
  • the surface hardness (HsA) of the rubber sample of Example 3 was maintained at about 80 until about 5 days after the start of immersion, and then the surface hardness decreased to 0 HsA on the 9th day. . From this, in the rubber sample of Example 3, the decrease in surface hardness was suppressed by the action of the hydrolysis inhibitor until about 5 days after the start of immersion, and after that, the surface hardness was suppressed due to the progress of hydrolysis of the degradable rubber component. It is assumed that the hardness has decreased.
  • Example 4 A rubber sample was prepared in the same manner as in Example 1, except that 4.5 parts by mass of a polymer carbodiimide compound was added as a hydrolysis inhibitor per 100 parts by mass of the degradable rubber component, and the surface hardness (HsA) was measured. did.
  • the measurement results of Example 4 are indicated by " ⁇ " (black squares) in FIG. It can be seen that the surface hardness (HsA) of the rubber sample of Example 4 became 0 (zero) 11 days after the start of immersion.
  • the rubber sample of Example 4 spontaneously disintegrated 11 days after the start of immersion, as in Example 1. This shows that the addition of the hydrolysis inhibitor suppressed the hydrolysis of the degradable rubber component. From the graph in FIG.
  • the surface hardness (HsA) of the rubber sample of Example 4 was maintained at about 80 until about 5 days after the start of immersion, and then the surface hardness decreased to 0 HsA on the 11th day. . From this, it can be seen that in the rubber sample of Example 4, the decrease in surface hardness was suppressed by the action of the hydrolysis inhibitor until about 5 days after the start of immersion, and after that, the surface hardness was suppressed due to the progress of hydrolysis of the degradable rubber component. It is assumed that the hardness has decreased. In addition, compared to Example 3, the rubber sample of Example 4 has a larger amount of hydrolysis inhibitor added, so even after the 5th day from the start of immersion, hydrolysis is suppressed due to the action of the hydrolysis inhibitor. It is presumed that the decrease in surface hardness (the slope of the graph) became more gradual, and the time from the start of immersion to natural collapse became longer.
  • the degradable rubber composition according to the present invention contains 40 parts by mass or more of a hydrolysis accelerator per 100 parts by mass of the degradable rubber composition, so that it can be easily immersed in water at 93°C. It has been shown that it is possible to form a rubber member that naturally disintegrates after a predetermined period of time.
  • the present invention includes the following gist.
  • the sealing member has the sealing performance as a rubber member, and after being continuously exposed to a fluid such as water for a predetermined period of time, it can be easily removed by breaking it into small pieces without applying external stress. It is possible to provide a degradable rubber composition capable of
  • (Purpose 2) It is a powder that shows basicity when it comes into contact with water, and contains a basic hydrolysis accelerator that promotes the hydrolysis of the rubber molecules when it comes into contact with water, and promotes the basic hydrolysis.
  • the agent may be contained in an amount of 1 part by mass or more based on 100 parts by mass of the decomposable rubber component.
  • the hydrolysis of the degradable rubber component can be further promoted.
  • the rubber molecules may have a mass average molecular weight of 10,000 or more.
  • the rubber member is intended to be formed from the degradable rubber composition according to any one of Purposes 1 to 3.
  • the sealing member is intended to include the rubber member of Purpose 4 as at least a part thereof.
  • the sealing member has the sealing performance as a rubber member, and after being continuously exposed to a fluid such as water for a predetermined period of time, it can be broken into small pieces without applying stress from the outside. It is possible to provide a rubber member and a sealing member that can be easily removed.
  • the method includes a kneading step of kneading raw materials containing an acidic hydrolysis accelerator that promotes the degradable rubber component, and the acidic hydrolysis accelerator is contained in an amount of 40 parts by mass or more based on 100 parts by mass of the degradable rubber component. Purpose.
  • the sealing member has the sealing performance as a rubber member, and after being continuously exposed to a fluid such as water for a predetermined period of time, it can be easily removed by breaking it into small pieces without applying external stress.
  • a method for producing a degradable rubber composition can be provided.

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  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : une composition de caoutchouc dégradable qui a des performances d'étanchéité requises pour des éléments en caoutchouc d'éléments d'étanchéité et qui, après avoir été exposée à un fluide, par exemple, de l'eau, sur une période donnée, peut se rompre en pièces même sans recevoir de contrainte externe et est ainsi rendue facilement amovible ; un élément en caoutchouc ; un élément d'étanchéité ; et un procédé de production de la composition de caoutchouc dégradable. La composition de caoutchouc dégradable comprend un composant de caoutchouc dégradable comprenant un matériau de caoutchouc pouvant être broyé composé de molécules de caoutchouc hydrolysables et un accélérateur d'hydrolyse acide qui est une poudre qui devient acide lors du contact avec l'eau et qui accélère l'hydrolyse des molécules de caoutchouc lors du contact avec l'eau. L'accélérateur d'hydrolyse acide est contenu en une quantité de 40 parties en masse ou plus pour 100 parties en masse du composant de caoutchouc dégradable.
PCT/JP2023/026218 2022-07-21 2023-07-18 Composition de caoutchouc dégradable, élément en caoutchouc, élément d'étanchéité et procédé de production d'une composition de caoutchouc dégradable WO2024019035A1 (fr)

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* Cited by examiner, † Cited by third party
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JPS6230110A (ja) * 1985-07-31 1987-02-09 Toyo Soda Mfg Co Ltd 常温硬化型弾性体組成物
JP2000230073A (ja) * 1999-02-08 2000-08-22 Nichias Corp 多孔質シリカ・ゴム複合材及びその製造方法
JP2011213374A (ja) * 2010-03-31 2011-10-27 Toyo Seikan Kaisha Ltd 生分解性多層容器
JP2014041973A (ja) * 2012-08-23 2014-03-06 Mitsubishi Heavy Ind Ltd 超音波厚みセンサ用酸化物系圧電材料粉末の製造方法、酸化物系圧電材料粉末、超音波厚みセンサの製造方法、および超音波厚みセンサ
JP2015108279A (ja) * 2013-05-31 2015-06-11 株式会社クレハ 分解性材料から形成されるマンドレルを備える坑井掘削用プラグ
JP2015143333A (ja) * 2013-12-27 2015-08-06 株式会社クレハ ダウンホールツール用分解性シール部材、ダウンホールツール、及び坑井掘削方法
JP2016098503A (ja) * 2014-11-19 2016-05-30 東洋製罐グループホールディングス株式会社 水圧破砕法を利用しての地下資源の採掘方法及び水圧破砕に用いる流体に添加される加水分解性ブロッキング剤
JP2017114989A (ja) * 2015-12-22 2017-06-29 株式会社クレハ 組成物、ダウンホールツール用組成物、ダウンホールツール用分解性ゴム部材、ダウンホールツール、及び坑井掘削方法
WO2018198881A1 (fr) * 2017-04-28 2018-11-01 株式会社クレハ Dispositif de fermeture de puits et procédé de fermeture de puits temporaire

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6230110A (ja) * 1985-07-31 1987-02-09 Toyo Soda Mfg Co Ltd 常温硬化型弾性体組成物
JP2000230073A (ja) * 1999-02-08 2000-08-22 Nichias Corp 多孔質シリカ・ゴム複合材及びその製造方法
JP2011213374A (ja) * 2010-03-31 2011-10-27 Toyo Seikan Kaisha Ltd 生分解性多層容器
JP2014041973A (ja) * 2012-08-23 2014-03-06 Mitsubishi Heavy Ind Ltd 超音波厚みセンサ用酸化物系圧電材料粉末の製造方法、酸化物系圧電材料粉末、超音波厚みセンサの製造方法、および超音波厚みセンサ
JP2015108279A (ja) * 2013-05-31 2015-06-11 株式会社クレハ 分解性材料から形成されるマンドレルを備える坑井掘削用プラグ
JP2015143333A (ja) * 2013-12-27 2015-08-06 株式会社クレハ ダウンホールツール用分解性シール部材、ダウンホールツール、及び坑井掘削方法
JP2016098503A (ja) * 2014-11-19 2016-05-30 東洋製罐グループホールディングス株式会社 水圧破砕法を利用しての地下資源の採掘方法及び水圧破砕に用いる流体に添加される加水分解性ブロッキング剤
JP2017114989A (ja) * 2015-12-22 2017-06-29 株式会社クレハ 組成物、ダウンホールツール用組成物、ダウンホールツール用分解性ゴム部材、ダウンホールツール、及び坑井掘削方法
WO2018198881A1 (fr) * 2017-04-28 2018-11-01 株式会社クレハ Dispositif de fermeture de puits et procédé de fermeture de puits temporaire

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