CN114426669B - Modified sepiolite fiber and graft copolymer thereof, tetrapropylfluoride rubber material and sealing rubber ring, and preparation method and application thereof - Google Patents
Modified sepiolite fiber and graft copolymer thereof, tetrapropylfluoride rubber material and sealing rubber ring, and preparation method and application thereof Download PDFInfo
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- CN114426669B CN114426669B CN202011043164.4A CN202011043164A CN114426669B CN 114426669 B CN114426669 B CN 114426669B CN 202011043164 A CN202011043164 A CN 202011043164A CN 114426669 B CN114426669 B CN 114426669B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The application discloses a modified sepiolite fiber and a graft copolymer thereof, a tetrapropylacetone rubber sizing material, a sealing rubber ring, a preparation method and application thereof. The modified sepiolite fiber of the present application is obtained by immersing the sepiolite fiber in a solution containing an alcoholysis aminosilane and an adhesion promoter. The modified sepiolite fiber of the application can realize the technical effect of fully dispersing the coronary reaction points on the sepiolite fiber. The modified sepiolite fiber and the tetrapropylacetone rubber form a graft copolymer, so that the obtained tetrapropylacetone rubber material has good hardness, modulus and stretching stress. And the sealing rubber ring prepared from the tetrapropylacetone rubber material can adapt to the complicated severe working condition of the underground oil field, and meets the sealing performance requirement of the tail pipe hanger.
Description
Technical Field
The application relates to a modified sepiolite fiber and a graft copolymer, a tetrapropylacetone rubber material, a sealing rubber ring, a preparation method and application thereof.
Background
In the field of oilfield exploitation technology, oil exploitation has gradually advanced to deeper floors, which means that the exploitation process of oil will face higher temperatures and pressures, which has been a problem for over 20 years. In fact, more than about 20% of oil fields belong to high pressure, high temperature (HPHT) wells. The high temperature and high pressure referred to herein mainly refer to temperatures above 170 ℃, pressures above 70MPa, and temperatures of some oil wells even above 200 ℃ or 225 ℃, which of course also belong to the high pressure and high temperature oil wells referred to in the present application.
In High Pressure High Temperature (HPHT) wells, the hanger needs to be lowered to below 7000m, at which time the bottom hole temperature is up to above 170 ℃ and the pressure is up to 50-100 MPa. In the bottom hole at this depth, the primary working media include mud, carbon dioxide, hydrogen sulfide, brine, and crude oil, among others. Such an operating environment places extremely high demands on the rubber sealing element on the liner hanger.
CN102010553a discloses a sealing ring rubber material and a mixing method thereof, which introduces a manufacturing method for double clutch sealing ring fluororubber, mainly describes improvement of technological properties and application thereof in the automobile oil seal market, and does not relate to application in complex medium (under the condition of mixing hydrogen sulfide, water, crude oil and sediment) of an oil field and High Pressure High Temperature (HPHT) environment.
CN103613886a discloses a high-temperature and high-pressure resistant fluororubber material, a preparation method and application thereof, which introduces a preparation method of a mixture of FKM and aramid pulp, but bisphenol vulcanized fluororubber adopted by the fluororubber material is not resistant to hydrogen sulfide and steam, so the fluororubber material cannot be used in high-temperature and high-pressure oil fields.
CN105111642a discloses a tetrapropylfluororubber with low compression set property and a preparation method thereof, and the main material involved in the process is the tetrapropylfluororubber, but the main material is the rubber, and is used together with or adopts a crosslinking auxiliary agent and other components which are not oil-proof, or has inherent defects of insufficient pressure resistance, insufficient high temperature resistance and the like, so that the sealing element cannot meet the requirement of the sealing element required by the liner hanger on the material property.
CN109749316a discloses a tetrapropylfluororubber composition resistant to high-temperature water environment and a preparation method, and the tetrapropylfluororubber composition disclosed in the application can be applied to an oilfield packer rubber barrel in high-temperature water environment for exploiting thick oil. However, this application employs lead oxide or the like to improve rubber stability, which not only severely pollutes corrosion metals, but also causes toxic and harmful effects on the environment. When the composition of the present application is used in a liner hanger, it can corrode structural parts, creating a significant potential hazard.
CN110157124a discloses a hydrogen sulfide corrosion resistant tetrapropylfluororubber composition and application thereof, which mainly adopts carbon nanotubes to improve extrusion resistance and decompression explosion resistance of rubber, is generally only suitable for manufacturing products with simple cross-sectional shapes, cannot meet the manufacturing requirements of complex products such as sealing rubber rings and the like in the application, and does not give performance data under high temperature and high pressure conditions.
CN101307165a discloses a heat-resistant fluororubber composition and vulcanized molded products thereof, which are mainly prepared by adding a proper amount of rare earth metal oxide to improve the heat aging resistance of fluororubber material, the performance of the rubber composition in a higher temperature environment is not examined, and the hardness of the composition is only about 80 degrees shore a, and is not suitable for a high pressure resistant environment.
CN108841017a discloses a heat treatment method for improving the crosslinking activity of tetrapropylacetone rubber, which adopts the technical scheme that the tetrapropylacetone rubber is treated for 0.5 to 3 hours in an oven at the temperature of 280-400 ℃, so that the crosslinking capacity of the tetrapropylacetone rubber is improved, and the effect is limited. And, an excessively high temperature may cause degradation of the molecular chains of the rubber and subsequent degradation of mechanical properties.
In summary, the disclosure of the prior art is not suitable for environments with high pressure and high temperature and complex working media, or has serious influence on the environment.
Disclosure of Invention
Aiming at the problems existing in the prior art, the application provides a modified sepiolite fiber, a graft copolymer thereof, a tetrapropylacetonate rubber material, a sealing rubber ring, a preparation method and application thereof. The modified sepiolite fiber provided by the application can realize the technical effect of fully dispersing various active reaction points, such as crown reaction points, on the sepiolite fiber after the sepiolite fiber reacts with the alcoholysis aminosilane and the adhesion promoter. The grafting reaction of the modified sepiolite fiber and the tetrapropylacetone rubber to obtain the graft copolymer can lead the crown energy reaction point to react at high temperature. The tetrapropylacetonate rubber sizing material obtained by the graft copolymer has good hardness, modulus and stretching stress. The sealing rubber ring prepared from the tetrapropylacetone rubber material can adapt to the high-temperature and high-pressure environment with the temperature of 180-225 ℃ and the pressure of 70-100 MPa, and can adapt to complex working media at the bottom of an oil field, so that the sealing rubber ring is used for sealing a tail pipe hanger, and has excellent sealing performance and long service life.
In a first aspect, the present application provides a modified sepiolite fiber obtained by immersing the sepiolite fiber in a solution containing an alcoholysis aminosilane and an adhesion promoter.
According to some embodiments of the modified sepiolite fibers of the present application, the alcoholysis aminosilane is obtained by dissolving the aminosilane in an alcohol solvent.
According to some embodiments of the modified sepiolite fibers of the present application, the alcohol solvent may be, but is not limited to: ethanol or propanol.
According to the preferred embodiment of the modified sepiolite fiber, the weight ratio of the alcohol solvent to the aminosilane is 100:1 to 3. For example, 100: 1. 100: 2. 100:3, and any value therebetween.
According to a preferred embodiment of the modified sepiolite fiber of the present application, the aminosilane is selected from at least one of diethylenetriamine propyl trimethoxysilane, bis- [3- (trimethoxysilicon) -propyl ] -amine, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and N- (2-aminoethyl) -3-aminopropyl methyl dimethoxy silane.
According to some embodiments of the modified sepiolite fibers of the present application, the adhesion promoter comprises titanium acetylacetonate and an epoxy resin.
According to a preferred embodiment of the modified sepiolite fiber of the present application, the epoxy resin is selected from bisphenol a type epoxy resins and/or glycidyl ester type epoxy resins.
According to a specific embodiment of the modified sepiolite fiber of the present application, the epoxy resin is selected from at least one of E-44 (6101), E-35 (637) and E-20 (601).
According to some embodiments of the modified sepiolite fibers of the present application, the sepiolite fibers have a specific surface area of 800 to 900m 2 /g。
According to some embodiments of the modified sepiolite fibers of the present application, the sepiolite fibers have a fiber length of 3 to 12mm. For example 3mm, 4mm, 6mm, 7mm, 8mm, 9mm, 12mm, and any value in between.
According to a preferred embodiment of the modified sepiolite fiber of the present application, the fiber length of the sepiolite fiber is 4 to 9mm.
According to some embodiments of the modified sepiolite fibers of the present application, the sepiolite fibers have an average length of 6 to 9mm. For example 6mm, 7mm, 8mm, 9mm, and any value in between.
According to some embodiments of the modified sepiolite fiber, the weight ratio of the alcohol solvent, the titanium acetylacetonate and the epoxy resin in the solution is 100:0.1 to 0.3:0.5 to 1.0. For example, 100:0.1:1.0, 100:0.2:0.5, 100:0.3:0.75, and any value therebetween.
According to some embodiments of the modified sepiolite fiber of the present application, the weight ratio of the sepiolite fiber to the solution is 0.5 to 1.5:2 to 4.
According to a preferred embodiment of the modified sepiolite fiber of the present application, in the modified sepiolite fiber, the weight ratio of the sepiolite fiber to the solution is 1:3.
according to some embodiments of the modified sepiolite fiber of the present application, the method of preparing the modified sepiolite fiber comprises the steps of:
and step A, dissolving the aminosilane in industrial grade ethanol, and carrying out alcoholysis reaction for 24 hours at room temperature to obtain the alcoholysis aminosilane. Wherein, the weight ratio of the industrial ethanol to the aminosilane is 100:1 to 3. Preferably, the weight ratio of the industrial ethanol to the aminosilane is 100:3.
and B, adding an adhesion promoter into the alcoholysis aminosilane obtained in the step A, and then stirring at a medium and low speed for more than 2 hours to obtain a solution. Wherein the adhesion promoter is titanium acetylacetonate and epoxy resin.
Preferably, in the solution, the weight ratio of the alcohol solvent, the titanium acetylacetonate and the epoxy resin is 100:0.1 to 0.3:0.5 to 1.0.
And C, immersing the sepiolite fiber into the solution obtained in the step B, stirring at a medium and low speed for 2 hours, distilling under reduced pressure to recover ethanol, and drying to obtain the modified sepiolite fiber.
Preferably, the weight ratio of the sepiolite fiber to the solution is 0.5-1.5: 2 to 4. Preferably, the weight ratio of the sepiolite fiber to the solution is 1:3.
in the preparation process of the modified sepiolite fiber, the technical effect of fully dispersing various crown energy reaction points on the sepiolite fiber can be realized through the reaction processes of the step A, the step B and the step C.
In a second aspect, the present application provides a graft copolymer of a tetrapropylfluororubber and a modified sepiolite fiber obtained by subjecting the tetrapropylfluororubber and the modified sepiolite fiber described above to a heat-refining reaction.
According to some embodiments of the graft copolymers of the present application, the tetrapropylating rubber is selected from at least one of tetrafluoroethylene-propylene polymer, tetrafluoroethylene-propylene-cure site monomer polymer, and ethylene-tetrafluoroethylene-perfluoromethyl vinyl ether-crosslinking site monomer polymer.
According to a specific embodiment of the graft copolymer according to the present application, the tetrapropylacetonate rubber is at least one of AFLAS100H, AFLAS S and ETP-600S.
According to some embodiments of the graft copolymer of the present application, the weight ratio of the tetrapropylfluororubber and the modified sepiolite fiber is 100:3 to 10. For example, 100:3. 100: 4. 100: 6. 100:10, and any value therebetween.
According to some embodiments of the graft copolymers of the present application, the temperature of the thermal refining reaction is 155 to 195 ℃ for 4 to 10 minutes.
According to a preferred embodiment of the graft copolymer according to the application, the temperature of the thermal refining reaction is 165 to 185℃for a period of 5 to 8 minutes.
The sepiolite fiber has high thermal stability, good modeling, low shrinkage, difficult cracking, high salinity resistance and good corrosion resistance. The sepiolite fiber has strong adsorption capacity, so that strong mechanical embedding force can be formed between the sepiolite fiber and the rubber matrix, and the sepiolite fiber has the capability of forming a physical crosslinking point by intertwining with a rubber molecular chain. Meanwhile, the sepiolite fiber has strong catalytic capability, and is favorable for forming a chemical grafting reaction point with rubber molecules.
However, the addition of sepiolite fibers can significantly reduce the elongation of the rubber material and can also lead to stress concentrations if the treatment is poorly dispersed. Based on the defect, the inventor finds that if sepiolite fiber is modified and then is subjected to chemical treatment with tetrapropylfluororubber, and the sepiolite fiber and the tetrapropylfluororubber are subjected to partial grafting reaction, the obtained graft copolymer of the tetrapropylfluororubber and the modified sepiolite fiber has strong mechanical properties at high temperature, and further the defect is avoided.
The graft copolymer obtained by grafting 3-10 wt% of modified sepiolite fiber into the tetrapropylacetone rubber can remarkably improve the dimensional stability, temperature resistance, pressure resistance and creep resistance of the tetrapropylacetone rubber used as a matrix.
According to some embodiments of the graft copolymers of the present application, the graft copolymers are prepared by:
adding the tetrapropylfluororubber to a high-temperature open mill, adjusting the roll spacing, adding the modified sepiolite fiber to carry out a heat-refining reaction after the tetrapropylfluororubber is wrapped, discharging the sheet by a scraper after the reaction is finished, and cooling and standing to obtain the graft copolymer of the tetrapropylfluororubber and the modified sepiolite fiber. Wherein the temperature of the heat refining reaction is 155-195 ℃ and the time is 4-10 minutes. Preferably, the temperature of the heat-refining reaction is 165-185 ℃ and the time is 5-8 minutes.
The preparation process of the graft copolymer can promote various active reaction points to react at high temperature, realizes the grafting reaction of the modified sepiolite fiber and the tetrapropylfluororubber, and endows the graft copolymer with excellent mechanical properties at high temperature.
In a third aspect the present application provides a tetrapropyle rubber compound comprising a graft copolymer of the tetrapropyle rubber and modified sepiolite fibers described above, a peroxide, a crosslinking aid, optionally a filler and a processing aid.
Some embodiments of the tetrapropofluororubber compounds according to the present application, wherein the composition of the substances is:
according to a preferred embodiment of the tetrapropylase rubber compound of the application, the composition of the substances is:
according to some embodiments of the tetraprop rubber compounds of the present application, the peroxide is an organic peroxide.
According to a preferred embodiment of the tetrapropylfluororubber compounds of the present application, said organic peroxide is selected from at least one of dicumyl peroxide, cumene hydroperoxide, p-methane hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydro-peroxide, di-tert-butyl peroxide, benzoyl peroxide, m-tolyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) -3-hexyne, 1, 3-di (tert-butyl peroxy isopropyl) benzene, 2, 5-dimethyl-2, 5-dibenzoyl peroxy hexane, (1, 3-tetramethylbutyl peroxy) -2-ethylhexyl peroxybenzoate, tert-butyl peroxylaurate, di (tert-butyl peroxy) adipate, di (2-ethoxyethyl peroxy) dicarbonate, bis (4-tert-butyl cyclohexyl peroxy) dicarbonate and bis (tert-butyl peroxy) diisopropylbenzene (vulcanizing agent BIBP).
According to a specific embodiment of the tetrapropylating fluororubber compound of the present application, said peroxide is di-tert-butyldiisopropylbenzene peroxide.
According to some embodiments of the tetraprop rubber compounds of the present application, the crosslinking aid is a polyfunctional unsaturated compound.
According to a preferred embodiment of the tetrapropylacetone rubber compound according to the application, the crosslinking auxiliary is selected from tri (methyl) allyl isocyanurate (TAIC) and/or tri (methyl) allyl cyanurate.
In the tetrapropofluororubber sizing material, the crosslinking auxiliary agent is compounded with other substances, so that the performances of mechanical strength, compression set and the like of the tetrapropofluororubber sizing material can be effectively improved.
According to some embodiments of the tetrapropofluororubber compounds of the present application, the filler is selected from at least one of semi-reinforcing carbon black, medium particle thermal black, spray carbon black, calcium silicate, diatomaceous earth, calcium carbonate, talc and molybdenum disulfide.
According to a preferred embodiment of the tetrapropofluororubber compounds of the present application, said filler is selected from semi-reinforcing carbon black and/or medium particle thermal black. Such as, but not limited to, carbon black N990 and carbon black N774.
In the tetrapropofluororubber sizing material, the filler is compounded with other substances, so that the hardness of the tetrapropofluororubber sizing material can be improved.
According to some embodiments of the tetrapropylating fluororubber compounds of the present application, said processing aid is a stearate.
According to a preferred embodiment of the tetrapropylacetone rubber compound according to the application, the processing aid is at least one of calcium stearate, sodium stearate and magnesium stearate.
According to some embodiments of the application, the preparation process of the tetrapropofluororubber compound is carried out by using an open mill or an internal mixer to prepare the raw materials through mixing.
According to the specific embodiment of the tetrapropylacetone rubber compound, the mixing process is as follows: and (3) putting raw rubber into a rubber tube for 10 times at room temperature, sequentially adding the raw materials according to the composition of the tetrapropylacetonate rubber material, uniformly mixing, and rolling out the sheet after at least 1300 s.
The tetrapropofluororubber sizing material prepared from the graft copolymer of the tetrapropofluororubber and the modified sepiolite fiber has good hardness, modulus and stretching stress.
The fourth aspect of the application provides a sealing rubber ring, which is prepared from the tetrapropylacetonate rubber material.
The sealing rubber ring prepared from the tetrapropylacetone rubber material has higher sealing performance and can effectively prolong the service life of the sealing rubber ring.
The fifth aspect of the application provides a method for preparing a sealing rubber ring, comprising the following steps:
and (3) one-stage vulcanization: carrying out primary vulcanization treatment on the tetrapropylacetone rubber material to obtain primary vulcanization products;
two-stage vulcanization: and performing secondary vulcanization treatment on the primary vulcanized product to obtain the sealing rubber ring.
According to some embodiments of the method for preparing a sealing rubber ring of the present application, the one-stage vulcanization conditions include: the pressure is 10-15 MPa, the temperature is 165-185 ℃ and the time is 10-35 min.
According to a preferred embodiment of the method for preparing a sealing rubber ring of the present application, the one-stage vulcanization conditions include: the pressure is 12-15 MPa, the temperature is 160-170 ℃ and the time is 10-35 min.
According to some embodiments of the method for preparing a sealing rubber ring of the present application, the conditions of the two-stage vulcanization include: the pressure is normal pressure, the temperature is 200-230 ℃, and the time is 3-4 h.
In the vulcanization process, the one-stage vulcanization process can lead the tetrapropylacetone rubber to achieve a certain degree of crosslinking, thereby playing a role in shaping. The two-stage vulcanization enables the low molecular weight substances in the tetrapropylacetonate rubber, such as H 2 O, HF, acetone and other reaction byproducts are released, so that the sufficient crosslinking of the tetrapropylacetone rubber is realized, and the mechanical property of the tetrapropylacetone rubber is improved.
According to some embodiments of the method of making a sealing gasket of the present application, the making is performed on a platen vulcanizer. Alternatively, the two-stage vulcanization process can also optionally be carried out in an oven.
The sixth aspect of the present application provides an application of the modified sepiolite fiber, the graft copolymer of the tetrapropylfluororubber and the modified sepiolite fiber, the tetrapropylfluororubber compound, the sealing rubber ring or the preparation method of the sealing rubber ring in oilfield exploitation technology, and more preferably in a tail pipe hanger. But is not limited thereto.
The application has the beneficial effects that:
(1) In the present application, the sepiolite fiber is modified by immersing the sepiolite fiber in a solution containing an alcoholysis aminosilane and an adhesion promoter, whereby the sepiolite fiber can be sufficiently dispersed with various reactive sites. The modified sepiolite fiber and the tetrapropylacetone rubber are subjected to chemical treatment, so that the obtained sealing rubber ring has the characteristics of high temperature resistance and high pressure resistance and is suitable for an underground complex working medium of an oil field.
(2) After the modified sepiolite fiber and the tetrapropylacetone rubber are subjected to chemical treatment and subjected to partial grafting reaction, the graft copolymer of the tetrapropylacetone rubber and the modified sepiolite fiber has stronger mechanical property at high temperature, the elongation of the tetrapropylacetone rubber is prevented from being reduced, and a stress concentration point does not exist.
(3) The tetrapropofluororubber sizing material obtained by compounding the graft copolymer of the tetrapropofluororubber and the modified sepiolite fiber, the peroxide and the crosslinking auxiliary agent, and optional filler and processing auxiliary agent has good hardness, modulus and stretching stress.
(4) The sealing rubber ring prepared by the tetrapropylacetone rubber sizing material can adapt to severe working conditions of high temperature and high pressure of 180-225 ℃ and 70-100 MPa in an oil field well and relatively complex working medium, and can well meet the sealing performance requirement of a tail pipe hanger.
Detailed Description
In order that the application may be more readily understood, the application will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the application.
The test method and the equipment used in the test are as follows:
(1) The performance of the tetrapropylethylene rubber compound is tested by adopting a method specified by GB/T531.1-2008, GB/T528-2009 and GB/T529-2008 standards.
(2) The performance test of the sealing rubber ring adopts a test method of ANSI/API SPEC 11D 13 rd edition.
The sources of reagents used in the present application are:
(1) Tetrapropylacetonate was purchased from AFLAS100H, a company of asahi.
(2) Sepiolite fiber was purchased from the new material company of Antai Hengxin as FKC100 model with a specific surface area of 850m 2 And/g, the fiber length is 7mm, and the average length is 7mm.
(3) The epoxy is purchased E-44 (6101).
Further, other reagents used in the present application are commercially available.
In examples 1-5 and comparative examples 1-2 below, different amounts of raw materials and different treatments were used to obtain tetrapropylacetonate rubber compounds, wherein the ingredients and amounts used are shown in tables 1 and 2.
Wherein Table 1 shows the ingredients and amounts used in the preparation of the modified sepiolite fibers of examples 1-5. Table 2 shows the ingredients and amounts used in the preparation of the tetrapropylacetonate gum.
Wherein the amounts shown in tables 1 and 2 are parts by weight.
TABLE 1
TABLE 2
[ example 1 ]
(1) Preparation of graft copolymers of tetrapropofluor rubber and modified sepiolite fibers
And step A, dissolving the diethylenetriamine propyl trimethoxysilane in industrial grade ethanol according to the concentration of 3 weight percent, and carrying out alcoholysis for 24 hours at room temperature.
And B, adding 0.1 g of titanium acetylacetonate and 1.0 g of epoxy resin into the product obtained in the step A containing 100g of ethanol, and stirring at a medium-low speed for more than 2 hours.
Step C, immersing sepiolite fibers into the solution obtained in the step B, wherein the weight ratio of the sepiolite fibers to the solution obtained in the step B is 1:3, stirring for 2 hours at medium and low speed, then carrying out reduced pressure distillation, recovering ethanol therein, and then drying at 80 ℃ to obtain the modified sepiolite fiber.
And D, adding 100g of tetrapropylacetone rubber on a high-temperature open mill at 175 ℃, adjusting the roll gap, adding 6g of modified sepiolite fiber after the tetrapropylacetone rubber is wrapped, carrying out heat refining for 7 minutes, discharging the sheet by a scraper, and cooling and standing.
(2) Preparation of tetrapropylfluororubber compounds
According to the components in Table 1, a graft copolymer of tetrapropofluor and modified sepiolite fiber, calcium stearate, carbon black N990, BIPB and TAIC were kneaded on an open mill according to the rubber manufacturing industry technique to obtain a tetrapropofluor rubber compound.
Wherein, the mixing process is carried out at room temperature, raw rubber is put into the mixer for 10 times, and after the raw rubber is put into the mixer, the raw rubber is rolled into sheets after 1300 s.
(3) Preparation of sealing rubber ring
And (3) standing the tetrapropylacetone rubber compound prepared by the steps for 24 hours, and then performing vulcanization treatment to prepare the sealing rubber ring. The vulcanization process involves a primary vulcanization and a secondary vulcanization.
The pressure of one-stage vulcanization is 12MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is 10min. The two-stage vulcanization is carried out under normal pressure, the vulcanization temperature is 230 ℃, and the vulcanization time is 4 hours.
[ example 2 ]
A packing was prepared by the same procedure as in example 1, except that the components and amounts shown in Table 1 were used.
[ example 3 ]
A packing was prepared by the same procedure as in example 1, except that the components and amounts shown in Table 1 were used.
[ example 4 ]
A packing was prepared by the same procedure as in example 1, except that the components and amounts shown in Table 1 were used.
[ example 5 ]
(1) Preparation of modified sepiolite fibers
And step A, dissolving the diethylenetriamine propyl trimethoxysilane in industrial grade ethanol according to the concentration of 3 weight percent, and carrying out alcoholysis for 24 hours at room temperature.
And B, adding 0.1 g of titanium acetylacetonate and 1.0 g of epoxy resin into the product obtained in the step A containing 100g of ethanol, and stirring at a medium-low speed for more than 2 hours.
Step C, immersing sepiolite fibers into the solution obtained in the step B, wherein the weight ratio of the sepiolite fibers to the solution obtained in the step B is 1:3, stirring for 2 hours at medium and low speed, then carrying out reduced pressure distillation, recovering ethanol therein, and then drying at 80 ℃ to obtain the modified sepiolite fiber.
(2) Preparation of tetrapropylfluororubber compounds
According to the components in Table 1, tetrapropofluor, modified sepiolite fiber, calcium stearate, carbon black N990, BIPB and TAIC were kneaded on an open mill according to the rubber manufacturing industry technique to obtain tetrapropofluor rubber compounds.
Wherein, the mixing process is carried out at room temperature, raw rubber is put into the mixer for 10 times, and after the raw rubber is put into the mixer, the raw rubber is rolled into sheets after 1300 s.
(3) Preparation of sealing rubber ring
And (3) standing the tetrapropylacetone rubber compound prepared by the steps for 24 hours, and then performing vulcanization treatment to prepare the sealing rubber ring. The vulcanization process involves a primary vulcanization and a secondary vulcanization.
The pressure of one-stage vulcanization is 12MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is 10min. The two-stage vulcanization is carried out under normal pressure, the vulcanization temperature is 230 ℃, and the vulcanization time is 4 hours.
Comparative example 1
(1) Preparation of tetrapropylfluororubber compounds
According to the components shown in Table 1, the respective components were kneaded on an open mill according to the rubber manufacturing industry technique to obtain a tetrafluoro-ethylene rubber compound. Wherein, the mixing process is carried out at room temperature, raw rubber is put into the mixer for 10 times, and after the raw rubber is put into the mixer, the raw rubber is rolled into sheets after 1300 s.
(2) Preparation of sealing rubber ring
And (3) standing the tetrapropylacetone rubber compound prepared by the steps for 24 hours, and then performing vulcanization treatment to prepare the sealing rubber ring. The vulcanization process involves a primary vulcanization and a secondary vulcanization.
The pressure of one-stage vulcanization is 12MPa, the vulcanization temperature is 170 ℃, and the vulcanization time is 10min. The two-stage vulcanization is carried out under normal pressure, the vulcanization temperature is 230 ℃, and the vulcanization time is 4 hours.
Comparative example 2
The seal ring was prepared by the same preparation method as comparative example 1 according to the components and amounts shown in table 1.
[ test case ]
The performance test results of the tetrapropylafluoro-rubber compounds and the sealing rubber rings prepared in the above examples and comparative examples are shown in Table 3.
TABLE 3 Table 3
Wherein, the sealing rubber rings prepared in examples 1-4 have the pressure drop of not more than 1MPa in 30 minutes under the conditions of 70MPa and 204 ℃ and have no bubbles. Example 5 because of the lack of a step of preparing a graft copolymer of tetrapropofluororubber and modified sepiolite fiber, the prepared tetrapropofluororubber compounds and sealing rings had poorer properties than examples 1 to 4, directly from each of the modified sepiolite fiber and tetrapropofluororubber as a preparation raw material.
Comparative example 1 and comparative example 2 passed the forward gas seal test at 70MPa for a packer at 204 ℃ and failed the reverse gas seal test at 32MPa when the pressure was increased by 42 MPa.
As can be seen from Table 3, after the modified sepiolite fiber and the tetrapropylfluororubber are subjected to graft polymerization, the performances of the prepared tetrapropylfluororubber compound and the sealing rubber ring prepared from the prepared tetrapropylfluororubber compound are obviously improved, and the sealing performance of the sealing rubber ring on a tail pipe hanger in a petroleum downhole tool can be better met under the severe working conditions of high pressure, high temperature and complex working medium during deep well oilfield exploitation.
What has been described above is merely a preferred example of the present application. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present application, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present application.
Claims (17)
1. A modified sepiolite fiber obtained by immersing a sepiolite fiber in a solution containing an alcoholysis aminosilane and an adhesion promoter;
the aminosilane is selected from at least one of diethylenetriamine propyl trimethoxysilane, bis- [3- (trimethoxysilicon) -propyl ] -amine, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and N- (2-aminoethyl) -3-aminopropyl methyl dimethoxy silane;
the adhesion promoter includes titanium acetylacetonate and an epoxy resin.
2. The modified sepiolite fiber according to claim 1, wherein the alcoholysis aminosilane is obtained by dissolving an aminosilane in an alcohol solvent; and/or the number of the groups of groups,
the sepiolite fiber has a specific surface area of 800-900 m 2 /g; and/or the number of the groups of groups,
the fiber length of the sepiolite fiber is 3-12 mm; and/or the number of the groups of groups,
the average length of the sepiolite fiber is 6-9 mm; and/or the number of the groups of groups,
in the solution, the weight ratio of the alcohol solvent, the titanium acetylacetonate and the epoxy resin is 100:0.1 to 0.3:0.5 to 1.0; and/or the number of the groups of groups,
in the modified sepiolite fiber, the weight ratio of the sepiolite fiber to the solution is as follows: 0.5 to 1.5:2 to 4.
3. The modified sepiolite fiber according to claim 2, wherein the weight ratio of the alcohol solvent to the aminosilane is 100:1 to 3; and/or the epoxy resin is selected from bisphenol a type epoxy resin and/or glycidyl ester type epoxy resin.
4. A graft copolymer of tetrapropylfluororubber and modified sepiolite fiber obtained by subjecting tetrapropylfluororubber and the modified sepiolite fiber of any one of claims 1 to 3 to a heat-refining reaction.
5. The graft copolymer of claim 4, wherein the tetrapropylarene is selected from at least one of tetrafluoroethylene-propylene polymer, tetrafluoroethylene-propylene-cure site monomer polymer, and ethylene-tetrafluoroethylene-perfluoromethyl vinyl ether-crosslinking site monomer polymer; and/or the number of the groups of groups,
the weight ratio of the tetrapropylacetonate to the modified sepiolite fiber is 100:3 to 10; and/or the number of the groups of groups,
the temperature of the heat refining reaction is 155-195 ℃ and the time is 4-10 minutes.
6. The graft copolymer of claim 5, wherein the temperature of the thermal refining reaction is 165 to 185℃for a period of 5 to 8 minutes.
7. A tetrapropofluororubber compound comprising a graft copolymer of tetrapropofluororubber and modified sepiolite fibers as defined in any one of claims 4 to 6, a peroxide, a crosslinking aid, optionally a filler and a processing aid.
8. The tetrapropofluororubber composition according to claim 7, wherein the composition of each substance is:
103-110 parts by weight of a graft copolymer of tetrapropylfluororubber and modified sepiolite fibers;
peroxide 0.5-10 weight portions;
3-7 parts by weight of a crosslinking auxiliary agent;
0-35 parts of filler;
0-3 parts of processing aid.
9. The tetrapropylafluoro rubber compound of claim 8, wherein said peroxide is used in an amount of 3 to 7 parts by weight.
10. The tetrapropofluororubber compound according to any of claims 7 to 9, wherein said peroxide is an organic peroxide; and/or the number of the groups of groups,
the cross-linking auxiliary agent is a multifunctional unsaturated compound; and/or the number of the groups of groups,
the filler is at least one selected from semi-reinforcing carbon black, medium-particle thermal cracking carbon black, spray carbon black, calcium silicate, diatomite, calcium carbonate, talcum powder and molybdenum disulfide; and/or the number of the groups of groups,
the processing aid is stearate.
11. The tetrapropofluororubber compound according to any of claims 7 to 9, characterized in that said crosslinking auxiliary is selected from tri (meth) allyl isocyanurate and/or tri (meth) allyl cyanurate; and/or the number of the groups of groups,
the processing aid is at least one of calcium stearate, sodium stearate and magnesium stearate.
12. A sealing gasket prepared from the tetrapropylase rubber compound of any one of claims 7-11.
13. The preparation method of the sealing rubber ring is characterized by comprising the following steps of:
and (3) one-stage vulcanization: subjecting the tetrapropylafluoro rubber compound of any one of claims 7-11 to a primary vulcanization treatment to obtain a primary vulcanized product;
two-stage vulcanization: and performing secondary vulcanization treatment on the primary vulcanized product to obtain the sealing rubber ring.
14. The method of preparing a sealing gasket of claim 13, wherein the one-stage vulcanization conditions include: the pressure is 10-15 MPa, the temperature is 165-185 ℃ and the time is 10-35 min; and/or, the conditions of the two-stage vulcanization include: the pressure is normal pressure, the temperature is 200-230 ℃, and the time is 3-4 h.
15. The method of preparing a sealing gasket of claim 14, wherein the one-stage vulcanization conditions include: the pressure is 12-15 MPa, the temperature is 165-170 ℃ and the time is 10-35 min.
16. Use of the modified sepiolite fiber of any one of claims 1 to 3, the graft copolymer of tetrapropylfluororubber and modified sepiolite fiber of any one of claims 4 to 6, the tetrapropylfluororubber compound of any one of claims 7 to 11, the sealing rubber ring of claim 12 or the sealing rubber ring produced by the production method of any one of claims 13 to 15 in oilfield exploitation technology.
17. The use according to claim 16 in a liner hanger.
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