JP2016535142A - Polyarylene ether sulfone oil and gas recovery article, preparation method and method of use - Google Patents

Abstract

An oil and gas recovery article comprising at least one portion made from a poly (aryl ether sulfone) polymer material comprising at least one poly (aryl ether sulfone) polymer, wherein the (t-PAES) polymer has the formula ( St): -E-Ar1-SO2- [Ar2- (T-Ar3) n-SO2] m-Ar4 wherein n and m are equal to or different from each other and are independently zero or 1-5. Each of Ar1, Ar2, Ar3 and Ar4, which is an integer and is equal to or different from each other, is an aromatic moiety, T is a bond or a divalent group, and E is a formula (Et): Wherein each R ′ is equal to or different from each other, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, Selected from the group consisting of rubonic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; j ′ is zero or an integer of 1 to 4)], and contains more than 50 mol% of repeating units (Rt). [Selection] Figure 1

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application gives priority to US Provisional Application No. 61/857034 filed July 22, 2013 and European Patent Application No. 13185207.1 filed September 19, 2013. The entire contents of these applications are hereby incorporated by reference for all purposes.

  The present invention is an article suitable for use in the oil / gas recovery industry comprising a polyarylene ether sulfone (PAES) polymer base material, wherein the (PAES) polymer comprises 4,4 ″ -terphenyl-p- It relates to an article comprising a moiety derived from the incorporation of a diol. The (PAES) polymer base material has improved mechanical properties, in particular a good balance between stiffness and ductility, good chemical resistance, high heat resistance (eg Tg> 230 ° C.), long term heat Stability, characterized by having a useful maximum Tm between 360 ° C and 420 ° C.

  The oil and gas market currently represents approximately one third of the polyetheretherketone (PEEK) market worldwide. Polyetheretherketone (PEEK) polymers are semi-crystalline polymers used primarily for a combination of properties, including their high heat and chemical resistance.

  Currently accessible oil fields are increasingly less productive; therefore, there is a need to start producing from less accessible oil fields, many of which are most deeply underwater and under high pressure, etc. Can be accompanied by difficult operating environment.

For example, articles suitable for use in oil and gas recovery applications, such as deep sea oil and gas recovery applications, particularly high pressure and high temperature [HP / HT, used below], high pressure, eg, pressures greater than 30,000 psi. These are exposed to high temperatures, for example, temperatures up to 260 ° C to 300 ° C, and harsh chemicals including acids, bases, superheated water / steam, and, of course, a wide variety of aliphatic and aromatic organics. Enduring harsh conditions is an important challenge for the oil and gas market. For example, enhancement of oil recovery technology involves injecting fluids such as water, water vapor, hydrogen sulfide (H ₂ S) or supercritical carbon dioxide (sCO ₂ ) into the wells, among others. In particular, sCO ₂ with similar solvation effects as n- heptane, for example, can cause swelling of the material in the seal, which, as a result affects their performance.

  Thus, oil and gas articles made from semi-crystalline PEEK polymers can no longer withstand pressures up to 30,000 psi and temperatures up to 300 ° C., and the articles are no longer suitable for the HP / HT oil and gas recovery applications described above. It has the disadvantage that it cannot be used.

As noted above, polymeric materials useful for providing articles suitable for use in the oil and gas recovery applications are therefore mechanical stiffness and integrity (eg, yield / integrity) at high pressures and temperatures of at least 300 ° C. tensile strength, maintenance or improvement of hardness and impact _{toughness), CO 2, H 2 S} , good chemical resistance when exposed to amines and other chemicals in particular the high pressures and temperatures, by gas and liquid absorbent It must have properties such as swelling and shrinkage, pressure resistance in high pressure oil / gas systems, gas and liquid diffusivity and long term thermal stability.

  Accordingly, it comprises at least one polymer material that can overcome the above-mentioned drawbacks, said polymer material being characterized by excellent mechanical properties (especially a good combination of high rigidity and ductility) and excellent rigidity and ductility Balanced, good processability, high chemical resistance, high heat resistance (eg Tg> 260 ° C.) and long-term thermal stability, and the polymer material has these improved properties as described above There remains a continuing need for articles suitable for use in oil and gas recovery applications that provide a final article having all of the above.

The present invention addresses the need detailed above and provides oil and gas recovery articles and methods of using it for oil and / or gas recovery comprising at least one poly (aryl ether sulfone). A polymer [(t-PAES) polymer], wherein the (t-PAES) polymer has the formula (S _t ):
^{_{-E-Ar 1 -SO 2 - [}} Ar 2 - (T-Ar 3) n -SO 2] m -Ar 4 - Formula (St)
[Where:
-N and m are equal to or different from each other, and are independently zero or an integer of 1 to 5;
Each of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ that is equal or different from each other and each occurrence is an aromatic moiety;
-T is a bond, or a one or two or more may also be divalent groups which contain a hetero atom; preferably T is a _{bond, -CH 2 -, - C (} O) -, - C (CH 3 ) ₂ −, —C (CF ₃ ) ₂ —, —C (═CCl ₂ ) —, —C (CH ₃ ) (CH ₂ CH ₂ COOH) —, and the formula:
Selected from the group consisting of
-E is the formula (E _t ):
Wherein each R ′ is equal to or different from each other, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate Selected from the group consisting of an alkali or alkaline earth metal phosphonate, an alkylphosphonic acid, an amine and a quaternary ammonium; j ′ is zero or an integer from 1 to 4)
belongs to]
Oil and gas recovery articles comprising at least one portion made of a poly (aryl ether sulfone) polymeric material (hereinafter (t-PAES) polymeric material), comprising more than 50 mol% of repeating units (R _t ), and It relates to the method of using it for oil and gas recovery.

FIG. 1 schematically shows a drilling rig installation. FIG. 2 is a pressure and temperature distribution curve obtained in the rapid gas decompression test.

Oil and Gas Recovery Article For the purposes of the present invention, the term “oil and gas recovery article” means any article that is designed for convenient use in oil and gas recovery applications, particularly HP / HT conditions. Is intended to be.

  For clarity, the term “part of oil and gas recovery article” is intended to mean a piece or part that is combined with the other to make up the entire oil and gas recovery article. Thus, the outer coating of oil and gas recovery articles falls within this range. Thus, at least one part of the oil and gas recovery article according to the present invention may be a coating.

  Representative examples of oil and gas recovery applications include, but are not limited to: (i) In particular, as described in US Pat. No. 5,662,170, the entire disclosure of which is incorporated herein by reference. Drilling and finishing of deep, relatively high temperature, relatively high pressure oil and gas wells, (ii) traditionally three stages: a primary oil recovery stage, a secondary or auxiliary oil recovery stage, and a tertiary or Oil and gas recovery method as subdivided into an enhanced oil recovery stage, (iii) Gas and oil collection processing applications, (iv) Combined gas and oil from said deep, relatively high temperature, relatively high pressure wells Transport, etc.

  All these uses as referred to herein above are known to those skilled in the art and should be understood in their general sense.

  Non-limiting examples of oil and gas recovery articles useful in the present invention are particularly as described in US Patent Application Publication No. 2001/0214920 A1, the entire disclosure of which is incorporated herein by reference. Drilling rigs; drilling rigs; in particular, compressor systems; pumping systems; motor systems, as described in US 2010/0239441 A1, the entire disclosure of which is incorporated herein by reference. Sensors such as reservoir sensors; control systems such as temperature and / or pressure; stimulation and flow control systems; in particular in US Pat. No. 6,655,456 B1, the entire disclosure of which is incorporated herein by reference. Liner hanger system as described; in particular, the entire disclosure of which is hereby incorporated by reference. And the like casing system; U.S. Pat. No. 7,874,356 of as described in B2 Pat, packer system incorporated into; pipe system, valve system, tubing (Tubing Talk) system.

  All these systems as referred to herein above are known to those skilled in the art and should be understood in their general sense.

  By the term “drilling rig” is used to drill an oil well, or natural gas extraction well, which may consist of a single article or of two or more components. Typically, the drilling rig components include, but are not limited to, a mud tank, shale shaker, mud pump, drill pipe, drill bit, drill line, and electrical cable tray.

  Non-limiting examples of pumping systems useful in the present invention include jet pump systems, submersible pumping systems, particularly US Pat. No. 6,863,124 B2, the entire disclosure of which is incorporated herein by reference. Especially electric submersible pumps and beam pumps as described in the book.

  Non-limiting examples of motor pumps useful in the present invention include mud motors, particularly as described in US Patent Application Publication No. 2012/0234603 A1, the entire disclosure of which is incorporated herein by reference. It is an assembly.

  Non-limiting examples of pipe systems useful in the present invention can include rigid and flexible tubes, flexible risers, pipe-in pipes, pipe liners, underwater jumpers, spools, and supply pipelines.

  Exemplary flexible pipes are, by way of example, WO 01/61232, US Pat. No. 6,123,114 and US Pat. No. 6,123,114, the entire disclosures of which are incorporated herein by reference. No. 085,799. Such flexible tubes can be used in particular for the transport of fluids where very high or very different water pressures are prevalent throughout the length of the tube, e.g. flexible running from the sea floor to the equipment at or near the sea level They can take the form of risers, which are also generally as pipes for the transfer of liquids or gases between various items of equipment or as pipes between equipment items close to the sea surface, as pipes laid deep in the seabed , Etc.

  Preferred pipe systems are pipes, flexible risers and pipe liners.

  By the term “valve” is meant any device for stopping or controlling the flow of liquid, gas or any other substance through a passage, pipe, inlet, outlet, etc. Non-limiting examples of valve systems useful in the present invention include choke valves, thermal expansion valves, check valves, ball valves, butterfly valves, diaphragm valves, gate valves, globe valves, knife valves, needle valves, pinch valves, Examples include piston valves, plug valves, poppet valves, spool valves, pressure reducing valves, sampling valves, and safety valves.

  At least one part of the oil and gas recovery article according to the invention comprises an article such as an attachment; a seal, in particular a seal ring, preferably a backup seal ring, a fastener, etc .; a snap fit part; Tracking element; Adjustment element; Conveying element; Frame element; Film; Switch; Connector; Wire, Cable; Compressor component such as bearing, housing, compressor valve and compressor plate, other than housing as used in oil and gas recovery items May be selected from a large list of articles such as shafts, shells, pistons, etc.

  In particular, the (t-PAES) polymer material is very well suited for the production of oil and gas recovery article seals, fasteners, cables, electrical connectors, housing parts.

  In a preferred embodiment, at least one part of the oil and gas recovery article according to the invention is advantageously an oil and gas recovery housing, a seal, an electrical connector or a cable.

  Cables in particular connect electrically different parts in oil and gas recovery articles, eg wires connecting different electrical connectors, wires connecting tools to connectors, equipment or other tools, equipment connectors, etc. It can be a wire connecting to a device or tool, a wire connecting a power source to a connector, device or tool. The cable can also advantageously be used to carry signals to a computer system.

  In particular in this preferred embodiment aspect, the cable is a coated wire or wire coating.

  By “oil and gas recovery housing” is meant one or more of the back cover, front cover, frame and / or skeleton of the oil and gas recovery article. The housing may be a single article or may include two or more components. By “framework” is meant a structural component to which other components of oil and gas recovery articles are attached. The scaffold may be an internal component that is not visible or only partially visible from the outside of the oil and gas recovery article.

  Typical fasteners are described by way of example in, but not limited to, WO 2010/112435, the entire disclosure of which is incorporated by reference, including but not limited to screw-type fasteners such as bolts, nuts, screws, headless positioning. There are screws, scribets, threaded studs and threaded bushings, and non-threaded fasteners such as pins, retaining rings, rivets, brackets and fixed washers, among others.

  Sealing of the components of the oil and gas recovery article is important and the seal is not only used in the part of the oil and gas recovery article that remains in the well after finishing, testing and fabrication of the well, but also oil and gas It can be said that it is used in all types of recovered articles. Thus, the seal needs to withstand these extreme conditions, as noted above, in a substantially indefinite time. It is worth mentioning that, except electronics, the seal can be considered the most valuable part of the oil and gas recovery article.

  In one embodiment of the invention, at least a portion of the oil and gas recovery article is a seal selected from the group consisting of a metal seal, an elastomeric seal, an intermetallic seal, and an elastomeric and intermetallic seal.

  Seals are typically used in drill bits, motor systems, particularly mud motors, reservoir sensors, stimulation and flow control systems, pump systems, especially electric submersible pumps, packers, liner hangers, tubing, casings and the like.

  Representative examples of seals include, but are not limited to, seal rings such as C rings, E rings, O rings, U rings, spring-loaded C rings, backup rings, etc .; fastener seals; piston seals, gasket O-seals; One-piece seal and labyrinth seal are included.

  In a particularly preferred embodiment, at least one part of the oil and gas recovery article according to the invention is a seal ring, preferably a backup seal ring.

  The weight of the (t-PAES) polymeric material is usually greater than 1%, greater than 5%, greater than 10%, preferably greater than 15%, greater than 20%, greater than 30%, based on the total weight of the oil and gas recovery article, More than 40%, more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, more than 95%, more than 99%.

  The oil and gas recovery article may consist of one part, i.e. it is a single component article. In that case, the single part preferably consists of (t-PAES) polymer material.

  Alternatively, the oil and gas recovery article may consist of several parts. In that case, either one part or several parts of the oil and gas recovery article may consist of (t-PAES) polymer material. If several parts of the oil and gas recovery article are made of (t-PAES) polymer material, each of them may be made of the very same (t-PAES) polymer material; Two may consist of different (t-PAES) polymer materials according to the present invention.

Method of recovering oil and / or gas using oil and gas recovery article According to another aspect of the invention, an oil comprising using at least one oil and gas recovery article as defined above A method for recovering gas and / or gas is provided herein.

  The method of the present invention is a method of recovering oil and / or gas from an underground formation, advantageously comprising using said oil and gas recovery article.

  The underground layer can be a deeply buried reservoir that can encounter temperatures close to 300 ° C., advantageously at a depth of more than 6,000 meters and a pressure of more than 1,500 bar; A gas article has all of the requirements and characteristics to qualify for a long period of time in this underground hellish place.

The method of the invention advantageously uses at least one oil and gas recovery article as defined above (a) at least for exploring or developing an oil and / or gas reservoir in a subterranean formation. Drilling one borehole;
(B) finishing at least one well using at least one oil and gas recovery article as defined above;
(C) It may include at least one operation selected from the group consisting of transferring oil and / or gas from the oil and / or gas reservoir in the underground layer to the ground surface.

  The work of drilling boreholes for exploring or developing oil and / or natural gas reservoirs generally involves the use of drilling rig equipment, which is an embodiment of oil and gas recovery articles as defined above. .

  FIG. 1 schematically illustrates a drilling rig installation. In this installation, the drill tube or string (5) acts as a conduit for drilling fluid; it is generally made up of hollow tubing joints connected together and stands vertically in an oil well. The drill bit (7) device is attached to the end of the drill string; this bit breaks apart the rock to be drilled. It also includes a jet through which drilling fluid exists. A rotary table (6) or top drive (not shown) rotates the drill string with the attached tool and bit.

  The mechanism or hoisting machine (13) houses the spool and its main function is to wind up / out the drill line and raise / lower the travel block.

  A mud pump (11) is used to circulate drilling fluid through the system; mud is drawn from a mud tank or mud pit (9) that provides a reserve reservoir of drilling fluid. Mud flows through the conduit 14 and the drill pipe (5) to the bit (7). Loaded with drilling material, it flows upward in the borehole and is drawn through conduit (12) and back to the muddy pit. The shale shaker (10) separates the drill dig from the drilling fluid, which then pumps back down the borehole.

  The facility may further include a device installed at the well head to prevent inadvertent leakage of fluid and gas from a borehole (not shown).

  Any of the components of a drilling rig as detailed above may be an oil and gas recovery article as detailed above, ie, as defined above (t− PAES) may include at least some portion that includes a polymeric material.

  The work b) of finishing the well is a work that encompasses all of the preparation or installation work necessary to bring the formation from the wellbore during work. This mainly involves preparing the bottom of the hole to the required specifications, plugging the production tubing and its associated downhole tool, and controlling the device, and drilling and stimulating as needed. Sometimes the process of plugging and cementing the casing is also included. In all of these single operations, an article comprising at least one portion comprising a (t-PAES) polymeric material as detailed above can be used.

(T-PAES) polymers The aromatic moieties in each of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ that are equal or different from each other and each occurrence preferably have the following formula:
(Where:
Each R _s is halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphone Independently selected from the group consisting of acid salts, alkyl phosphonates, amines and quaternary ammonium;
-K is zero or an integer from 1 to 4; k 'is zero or an integer from 1 to 3)
Follow.

In the repeating unit (R _t ), each phenylene moiety is independently independent of 1,2-, 1,4- or 1,3-linkage to another moiety different from R or R ′ in the repeating unit. You may have. Preferably, the phenylene moieties have 1,3- or 1,4-linkages, more preferably they have 1,4-linkages.

Further, in the repeat unit (R _t ), j ′, k ′ and k are zero each time they appear, ie the phenylene moiety has no substituents other than those that allow linkage in the polymer backbone. I don't have it.

Preferred repeating units (R _t ) are represented by the following formulas (S _t -1) to (S _t -4):
(Where
Each of -R 'is equal to or different from each other, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, Selected from the group consisting of alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines and quaternary ammonium;
-J 'is zero or an integer from 1 to 4,
-T is a bond, or a one or two or more may also be divalent groups which contain a hetero atom; preferably T is a _{bond, -CH 2 -, - C (} O) -, - C (CH 3 ) ₂ −, —C (CF ₃ ) ₂ —, —C (═CCl ₂ ) —, —C (CH ₃ ) (CH ₂ CH ₂ COOH) —, and the formula:
Selected from the group consisting of
Selected from the group consisting of:

The above repeating units of preferred embodiments (R _t -1) to (R _t -4) may each be present alone or in a mixture.

More preferred repeating units (R _t ) are represented by the following formulas (S ^′ _t −1) to (S ^′ _t -3):
Selected from the group consisting of:

The most preferred repeating unit (R _t ) is of the formula (S ^′ _t −1), as shown above. According to certain embodiments, the (t-PAES) polymer, as detailed above, has the formula (K _a ) in addition to the repeating unit (R _t ), as detailed above. :
^{-E-Ar 5 -CO- [Ar 6} - (T-Ar 7) n -CO] m -Ar 8 - ( wherein _K a)
(Where:
-N and m are equal or different from each other and are independently zero or an integer of 1 to 5;
Each of Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ is equal to or different from each other and each occurrence is an aromatic moiety;
-T is a bond, or a one or two or more may also be divalent groups which contain a hetero atom; preferably T is a _{bond, -CH 2 -, - C (} O) -, - C (CH 3 ) ₂ −, —C (CF ₃ ) ₂ —, —C (═CCl ₂ ) —, —C (CH ₃ ) (CH ₂ CH ₂ COOH) —, and the formula:
Selected from the group consisting of
-E is of the formula (E _t ) as detailed above
Of repeating units (R _a ).

The repeating unit (R _a ) is in particular represented by the following formula (K _a -1) or formula (K _a -2):
(Where
Each of -R 'is equal to or different from each other and each of R' is halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonic acid Selected from the group consisting of salts, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines and quaternary ammonium;
-J 'is zero or an integer from 1 to 4)
Can be selected.

A more preferable repeating unit (R _a ) is represented by the following formula (K ′ _a -1) or formula (K ′ _a -2):
Selected from the group consisting of:

According to one particular embodiment, the (t-PAES) polymer, as detailed above, is in addition to the repeat unit (R _t ), as detailed above, in addition to Ar—SO ₂ — A repeating unit (R _b ) comprising an Ar ′ group (Ar and Ar ′ are the same or different from each other and an aromatic group), generally represented by the formula (S1):
(S1): —Ar ⁹ — (T′—Ar ¹⁰ ) _n —O—Ar ¹¹ —SO ₂ — [Ar ¹² — (T—Ar ¹³ ) _n —SO ₂ ] _m —Ar ¹⁴ —O—
(Where:
-Ar ⁹ , Ar ¹⁰ , Ar ¹¹ , Ar ¹² , and Ar ¹⁴ are equal or different from each other and each occurrence and are independently an aromatic mononuclear or polynuclear group;
-T and T 'are equal or different from each other and each occurrence, are independently a bond, or a divalent group that may contain one or more heteroatoms; preferably T' is _{bond, -CH 2 -, - C (} O) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - C (= CCl 2) -, - C (CH 3) (CH 2 _{CH 2 COOH) -, - SO} 2 -, and wherein:
Selected from the group consisting of
Preferably T is a bond, —CH ₂ —, —C (O) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C (═CCl ₂ ) —, —C (CH _{3) (CH 2 CH 2 COOH} ) -, and wherein:
Selected from the group consisting of
-N and m are equal to or different from each other and independently include a repeating unit (R _b ) according to zero or an integer from 1 to 5.

The repeating unit (R _b ) is particularly represented by the following formula (S1-A) to formula (S1-D):
(Where:
Each of -R 'is equal to or different from each other, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, Selected from the group consisting of alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines and quaternary ammonium;
-J 'is zero or an integer from 0 to 4;
-T and T ', equal or different from each other, coupled, or one or is 2 or more may also be divalent groups which contain a hetero atom; preferably T' is a bond, -CH 2 _-, - _{C (O) -, - C} (CH 3) 2 -, - C (CF 3) 2 -, - C (= CCl 2) -, - C (CH 3) (CH 2 CH 2 COOH) -, - SO _2- and the formula:
Selected from the group consisting of
Preferably T is a bond, —CH ₂ —, —C (O) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C (═CCl ₂ ) —, —C (CH _{3) (CH 2 CH 2 COOH} ) -, and wherein:
Selected from the group consisting of
Can be selected from the group consisting of:

In the repeating unit (R _b ), each phenylene moiety independently has a 1,2-, 1,4- or 1,3-linkage to another moiety different from R ′ in the repeating unit. Also good. Preferably, the phenylene moieties have 1,3- or 1,4-linkages, more preferably they have 1,4-linkages. Furthermore, in the repeat unit (R _b ), j ′ is zero each time it appears, ie the phenylene moiety has no substituents other than those that allow linkage in the polymer backbone.

According to certain embodiments, the (t-PAES) polymer as detailed above is in addition to the repeat unit (R _t ) as detailed above, in addition to Ar—C (O) — A repeating unit (R _c ) comprising an Ar ′ group (Ar and Ar ′ are the same or different from each other and an aromatic group), and is generally represented by the following formulas (JA) to (JL): :
(Where:
Each of -R 'is equal to or different from each other, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, Selected from the group consisting of alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines and quaternary ammonium;
-J ′ comprises a repeating unit (R _c ) selected from the group consisting of zero or an integer from 0 to 4.

In the repeating unit (R _c ), each phenylene moiety may have a 1,2-, 1,4- or 1,3-linkage to another moiety different from R ′ in the repeating unit. Preferably, the phenylene moieties have 1,3- or 1,4-linkages, more preferably they have 1,4-linkages.

Further, in the repeat unit (R _c ), j ′ is zero each time it appears, that is, the phenylene moiety has no substituents other than those that allow linkage in the polymer backbone.

As noted above, the (t-PAES) polymer has a repeat unit (R _t ) of the formula (S _t ) as detailed above, more than 50 mol%, preferably more than 60 mol%, more preferably Complementing to 100 mol%, including in an amount greater than 70 mol%, even more preferably greater than 80 mol%, most preferably greater than 90 mol%, is generally a repeat unit (R _a as detailed above). ), And / or repeating units (R _b ) and / or repeating units (R _c ) as detailed above.

Even more preferably, essentially all of the (t-PAES) polymer repeat units are such that the repeat unit is a repeat unit (R _t ) and there may be chain defects, or very small amounts of other units, It is understood that these latter do not substantially change the properties of the (t-PAES) polymer. Most preferably, all of the repeating units of the (t-PAES) polymer are repeating units (R _t ). Excellent results were obtained when the (t-PAES) polymer was a polymer in which all of the repeat units are repeat units (R _t ) as detailed above.

For the purpose of providing polymers that are particularly suitable for use in oil and gas recovery articles, the (t-PAES) polymers of the present invention are advantageously at least 13,000, preferably at least 25000, more preferably at least 38000. Number average molecular weight (M _n ).

(T-PAES) the upper limit of the number average molecular weight of the polymer (M _n) is not particularly critical, is chosen by a person skilled in the art in view of the final field of use.

In one embodiment of the invention, the t-PAES polymer is advantageously 125000 or less, preferably 95000 or less, preferably 90000 or less, preferably 80000 or less, preferably 75000 or less, preferably 70000 or less, preferably 60000 or less, Preferably it has a number average molecular weight ( _Mn ) of 56000 or less.

In one embodiment of the invention, the t-PAES polymer has a number average molecular weight ( _Mn ) advantageously in the range of 13000-125000, preferably in the range of 25000-80000, preferably in the range of 38000-80000.

(T-PAES) polymers having such a specific molecular weight (M _n ) range have excellent ductility (ie, high tensile elongation), good toughness while maintaining high Tg, and good crystallinity and good It was found to have chemical resistance.

The expression “number average molecular weight (M _n )” is used herein in accordance with its ordinary meaning and is mathematically represented as:
(Wherein, M _i is the discrete value for the molecular weight of the polymer molecules, N _i is the number of polymer molecules having a molecular weight M _i, in this case, the weight of all the polymer molecules in the? M _i N _i And the total number of polymer molecules is ΣN _i ).

M _n can be appropriately measured by gel permeation chromatography (GPC) calibrated with polystyrene standards.

Another molecular parameter that can be measured in particular by GPC is the weight average molecular weight (M _w ):
(Wherein, M _i is the discrete value for the molecular weight of the polymer molecules, N _i is the number of polymer molecules having a molecular weight M _i, in which case, the weight of the polymer molecules having a molecular weight M _i is M _i it is N _i).

For purposes of the present invention, the polydispersity index (PDI) is expressed herein as the ratio of weight average molecular weight (M _w ) to number average molecular weight (M _n ).

  Details of GPC measurements are described in detail in the method descriptions given in the experimental section, and in particular in our co-pending US provisional patent application.

  The (t-PAES) polymers of the present invention advantageously have a polydispersity index (PDI) of greater than 1.90, preferably greater than 1.95, more preferably greater than 2.00.

  The (t-PAES) polymers of the present invention generally have a polydispersity index of less than 4.0, preferably less than 3.8, more preferably less than 3.5.

  Furthermore, some other analytical methods can be used as indirect methods for the determination of molecular weight, particularly including viscosity measurements.

  Furthermore, some other analytical methods can be used as indirect methods for the determination of molecular weight, particularly including viscosity measurements.

  In one embodiment of the present invention, the (t-PAES) polymer of the present invention is measured using a parallel plate viscometer (eg, TA ARES RDA3 model) according to ASTM D4440, at 410 ° C. and 10 rad / sec shear. Preferably at least 0.7 kPa. s, preferably at least 1.25 kPa. s, more preferably at least 2.3 kPa. having a melt viscosity of s. The (t-PAES) polymers of the present invention advantageously have a maximum of 46 kPa.s measured at 410 ° C. and a shear rate of 10 rad / sec as measured using a parallel plate viscometer (eg, TA ARES RDA3 model) according to ASTM D4440. s, preferably up to 34 kPa. s, more preferably up to 25 kPa. having a melt viscosity of s.

  In another embodiment of the invention, the (t-PAES) polymer of the invention is advantageously at least 2 measured at 410 ° C. and a shear rate of 1 rad / sec as measured using a parallel plate viscometer according to ASTM D4440. .2 kPa. s, preferably at least 4.1 kPa. s, more preferably at least 7.4 kPa. having a melt viscosity of s. The (t-PAES) polymers of the present invention advantageously have a maximum of 149 kPa.s at 410 ° C. and a shear rate of 1 rad / sec as measured using a parallel plate viscometer (eg, TA ARES RDA3 model) according to ASTM D4440. s, preferably up to 111 kPa. s, more preferably up to 82 kPa. having a melt viscosity of s.

  The (t-PAES) polymers of the present invention advantageously have a glass transition temperature of at least 210 ° C, preferably at least 220 ° C, more preferably at least 230 ° C.

  The glass transition temperature (Tg) is generally determined by DSC according to ASTM D3418.

  The (t-PAES) polymers of the present invention advantageously have a melting temperature of at least 330 ° C, preferably 340 ° C, more preferably at least 350 ° C. The (t-PAES) polymers of the present invention advantageously have a melting temperature of less than 430 ° C, preferably less than 420 ° C, more preferably less than 410 ° C.

  Melting temperature (Tm) is generally determined by DSC according to ASTM D3418.

  It is known that the crystallinity of polymers is characterized by their crystallinity.

  Crystallinity can be determined by various methods known in the art, particularly by wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC).

  The Applicant has found that (t-PAES) polymers as detailed above are particularly well suited for providing oil and gas recovery articles with very high crystallinity.

  Crystallinity can advantageously be measured by DSC on compression molded samples of the (t-PAES) polymer of the present invention.

  According to the invention, the molded part of the (t-PAES) polymer advantageously has a crystallinity of more than 5%, preferably more than 7%, more preferably more than 8%.

  The production of the (t-PAES) polymer of the present invention is not particularly limited. The (t-PAES) polymer can be prepared in particular as described in EP 0 383 600 A2, or in particular as described in our co-pending US provisional patent application. .

  Applicants have found that (t-PAES) polymers as detailed above have (1) high Tg and Tm for thermal performance, (2) high resistance to aggressive chemicals such as sulfuric acid in particular. It has been found to be particularly well suited for providing oil and gas recovery articles that are chemical, (3) resistant to rapid decompression, and (4) thermoplastic.

t- (PAES) polymer material (t-PAES) polymer material comprises (t-PAES) polymer based on the total weight of (t-PAES) polymer material, at least 10%, at least 30%, at least 40%, Or it may comprise at least 50% by weight. Preferably, the (t-PAES) polymer material comprises (t-PAES) polymer in a weight of at least 70%, based on the total weight of the (t-PAES) polymer material. More preferably, the (t-PAES) polymer material has a weight of at least 90%, if not at least 95%, based on the total weight of the (t-PAES) polymer material. Including. Even more preferably, the (t-PAES) polymer material consists essentially of the (t-PAES) polymer. Most preferably it consists essentially of (t-PAES) polymer.

  For the purposes of the present invention, the expression “consisting essentially of” means that any additional component different from the (t-PAES) polymer, as detailed above, is the sum of the composition (C). It should be understood that it is present in an amount of up to 1% by weight, based on weight, so that it does not substantially change the advantageous properties of the composition.

  (T-PAES) polymeric materials generally comprise (i) colorants such as dyes in particular, (ii) pigments such as in particular titanium dioxide, zinc sulfide and zinc oxide, and (iii) light stabilizers such as UV stabilizers. (Iv) heat stabilizers, (v) antioxidants, such as, in particular, organic phosphites and phosphonites, (vi) acid scavengers, (vii) processing aids, (viii) nucleating agents, (ix) internal lubrication Agents and / or external lubricants, (x) flame retardants, (xi) smoke suppressors, (x) antistatic agents, (xi) antiblocking agents, (xii) conductive additives such as carbon black and carbon in particular Selected from the group consisting of nanofibrils, (xiii) plasticizers, (xiv) fluidity improvers, (xv) extenders, (xvi) metal deactivators, and combinations comprising one or more of the aforementioned additives. It is the may include a further optionally one or more than one additional material different (I) and (t-PAES) polymer.

  When one or more additional raw materials (I) are present, their total weight is usually less than 20%, preferably less than 10%, more preferably based on the total weight of the polymer composition (C) Is less than 5%, even more preferably less than 2%.

  Optionally, the (t-PAES) polymer material comprises greater than 80% by weight of (t-PAES) polymer material, provided that (t-PAES) polymer is the only (t-PAES) polymer material And one or more additional raw materials (I) may be present therein, these components comprising the relevant mechanical properties of the (t-PAES) polymer material and Provided that it does not dramatically affect toughness.

  The expression “polymer component” should be understood to encompass compounds characterized by repeating linking units according to their usual meaning, ie, typically having a molecular weight of 2000 or greater.

  The (t-PAES) polymer material may further comprise at least one reinforcing filler. Reinforcing fillers are well known by those skilled in the art. They are preferably selected from fibrous and particulate fillers that are different from the pigments as defined above. More preferably, the reinforcing filler is a mineral filler (talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, etc.), glass fiber, carbon fiber, synthetic polymer fiber, aramid fiber, aluminum fiber, titanium fiber, It is selected from magnesium fiber, boron carbide fiber, rock wool fiber, steel fiber, wollastonite and the like. Even more preferably, it is selected from mica, kaolin, calcium silicate, magnesium carbonate, glass fiber, carbon fiber, wollastonite and the like.

Preferably, the filler is selected from fibrous fillers. A particular class of fiber filler consists of whisker, ie single crystal fibers made from various raw materials such as Al ₂ O ₃ , SiC, BC, Fe and Ni.

  In one embodiment of the invention, the reinforcing filler is selected from wollastonite and glass fiber. Of the fibrous fillers, glass fibers are preferred; they include chopped strand A, as described in Additives for Plastics Handbook, 2nd edition, John Murphy, chapter 5.2.3, pages 43-48. -, E-, C-, D-, S-, T- and R-glass fibers are included.

  Glass fibers optionally included in a polymer (t-PAES) polymer material may have a circular or non-circular cross section (such as an elliptical or rectangular cross section).

  When the glass fibers used have a circular cross section, they preferably have an average glass fiber diameter of 3 to 30 μm, particularly preferably those of 5 to 12 μm. Various types of glass fibers having a circular cross section are commercially available depending on the type of glass from which they are made. Particular mention may be made of glass fibers made from E- or S-glass.

  Good results have been obtained with a non-circular and cross-section standard E-glass material. Excellent results have been obtained for polymer compositions with round cross-section S-glass fibers, especially when using a 6 μm diameter round cross-section (E-glass or S-glass).

  In another embodiment of the invention, the reinforcing filler is carbon fiber.

  As used herein, “carbon fiber” is intended to include graphitized, partially graphitized and non-graphitized carbon reinforcing fibers, or mixtures thereof. The carbon fibers useful in the present invention can be advantageously obtained by heat treatment and pyrolysis of various polymer precursors such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamide or phenolic resin; Useful carbon fibers may also be obtained from pitch materials. The term “graphite fiber” is intended to mean a carbon fiber obtained by high temperature pyrolysis (greater than 2000 ° C.) of carbon fiber, where the carbon atoms are located in a manner similar to the graphite structure. The carbon fibers useful in the present invention are preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers, and mixtures thereof.

  The weight of the reinforcing filler is advantageously less than 60%, more preferably less than 50%, even more preferably less than 45% by weight, based on the total weight of the (t-PAES) polymer material. Most preferably it is less than 35% by weight.

  Preferably, the reinforcing filler is 10 to 60 wt%, preferably 20 to 50 wt%, preferably 25 to 45 wt%, most preferably 25 to 25 wt%, based on the total weight of the polymer (t-PAES) polymer material. Present in an amount ranging from 35% by weight.

  The (t-PAES) polymer material is optionally combined with at least one (t-PAES) polymer, for example by dry blending, suspension or slurry mixing, solution mixing, melt mixing, or a combination of dry blending and melt mixing. Can be prepared by a variety of methods involving intimate mixing of the reinforcing filler and optionally the additional raw material (I) desired in the polymeric material.

  Typically, the dry blending of the (t-PAES) polymer, preferably as detailed above in the powdered state, optionally a reinforcing filler, and optionally an additional raw material (I) is in particular a Henschel type. Performed by using high strength mixers, such as mixers and ribbon mixers, physical mixtures, in particular at least one (t-PAES) polymer, optionally reinforcing fillers, and optionally additional raw materials (I ) Powder mixture.

  Alternatively, intimate mixing of at least one (t-PAES) polymer, optionally reinforcing filler, and optionally additional raw material (I) desired in the polymer material can be achieved with a single-axis or multi-axis rotation mechanism. To obtain a physical mixture.

  Instead, slurry mixing of the (t-PAES) polymer as detailed above, optionally reinforcing filler, and optionally additional feedstock (I) can be carried out in a suitable liquid stirrer such as, for example, methanol. Is first slurried with the polymer (T-PAES) in powder form, optionally with polymer (T), optionally with reinforcing filler, and optionally with additional raw material (I), Filtering off the liquid, resulting in a powder mixture of at least one (t-PAES) polymer, optionally reinforcing filler, and optionally additional raw material (I).

  In another embodiment, solution mixing of the (t-PAES) polymer as detailed above, optionally a reinforcing filler, and optionally additional feedstock (I) may be, for example, diphenylsulfone, benzophenone, It is carried out using a stirrer in a suitable solvent or solvent blend such as 4-chlorophenol, 2-chlorophenol, meta-cresol. Most preferred are diphenyl sulfone and 4-chlorophenol.

  Following the physical mixing step according to one of the aforementioned techniques, a physical mixture of at least one (t-PAES) polymer, optionally a reinforcing filler, and optionally an additional raw material (I), in particular, is obtained. The powder mixture is typically melt processed by methods known in the art, including, for example, melt forming processes such as, for example, compression molding, injection molding, extrusion, etc. to obtain the oil and gas recovery articles described above. Or a finished oil and gas recovery article.

  The physical mixture so obtained, in particular the powder mixture obtained, is a (t-PAES) polymer as detailed above, a reinforcing filler as detailed above, and optionally, Other raw materials (I) may be included in weight ratios as detailed above, or used as a masterbatch and in subsequent processing steps (t-PAES) polymers as detailed above Can be a concentrated mixture to be diluted with additional amounts of reinforcing fillers as detailed above, and optionally other ingredients (I). For example, the resulting physical mixture can be extruded into a stock shape, such as a slab or rod, from which the final part can be machined. Alternatively, the physical mixture can be compression molded into a finished part of the oil and gas recovery article or from a stock shape from which the finished part of the oil and gas recovery article can be machined.

  It is also possible to produce the composition of the present invention by further melt blending a powder mixture as described above. As noted above, melt blending can be applied to a powder mixture as detailed above or to a (t-PAES) polymer as detailed above, a reinforcing filler as detailed above. , And optionally, can be performed directly on the other raw materials (I). Conventional melt compounding equipment may be used, such as co-rotating and reversing extruders, single screw extruders, coniders, disk-pack processors and various other types of extrusion equipment. Preferably, an extruder, more preferably a twin screw extruder may be used.

  Optionally, the compounding screw design, e.g., flight pitch and width, clearance, length and operating conditions, advantageously allows the powder mixture or raw material as detailed above to be advantageously completely melted, In order to advantageously obtain a homogeneous distribution of the various raw materials, it is selected such that sufficient heat and mechanical energy are supplied. Provided that optimum mixing is achieved between the bulk polymer and the filler content. Advantageously, it is possible to obtain non-ductile strand extrudates of the (t-PAES) polymer material of the present invention. Such strand extrudates can be chopped, for example with a rotating knife, after a cooling time on a conveyor with water spray. Thus, for example, polymeric materials that may be present in the form of pellets or beads (t-PAES) can then be further used in the manufacture of the oil and gas recovery article portions described above.

  Another object of the present invention is to provide a method for the manufacture of parts of the oil and gas recovery articles described above. Such a method is not particularly limited. (T-PAES) polymeric materials may generally be processed by injection molding, extrusion, or other shaping techniques.

  In one embodiment of the present invention, the above-described part of oil and gas recovery article, or method for the manufacture of oil and gas recovery article, comprises the steps of injection molding and solidification of (t-PAES) polymer material.

  In another embodiment, the above-described part of the oil and gas recovery article or the method for the production of oil and gas recovery article comprises a coating step.

  For example, the (t-PAES) polymeric material is preferably extruded around the wire by using any suitable coating method, particularly as disclosed in US Pat. No. 4,588,546. By coating to form a coated wire, it can be applied to the wire as a coating. As disclosed in US Pat. No. 4,588,546, the wire coating can be applied to the wire by any suitable method, such as by extrusion coating, especially around the wire.

  Techniques for manufacturing wire coatings are well known in the art.

  In another embodiment of the present invention, the parts of the oil and gas recovery article as described above, or the method for the production of oil and gas recovery article as described above are standard in parts having any type of size and shape. Machining a shaped structure. Non-limiting examples of the standard shaped structure include, in particular, plates, rods, slabs and the like. The standard shaped structure can be obtained by extrusion or injection molding of a polymer composition (t-PAES) polymer material.

  Applicants are now aware that portions of the oil and gas recovery articles and finished oil and gas recovery articles comprising the (t-PAES) polymer material of the present invention are (1) high Tg and Tm for thermal performance, ( 2) It has been found to have high chemical resistance to chemicals important to oil fields, including sulfuric acid, (3) resistance to rapid decompression, and (4) thermoplastic properties. Thus, the article can be successfully used in HPHT oil and gas environments while at the same time having a more cost effective article molding process.

  In the event that any disclosure of patents, patent applications, and publications incorporated herein by reference contradicts the description of this application to the extent that the terms may be obscured, the description shall control.

  The present invention will now be described in greater detail with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.

Raw materials Further purification by washing with 1,1 ′: 4 ′, 1 ″ -terphenyl-4,4 ″ -diol, commercially available from Yonghi Chemicals, China, ethanol / water (90/10) at reflux did. The purity of the resulting material was shown to be greater than 94.0% as measured by gas chromatography as detailed below.

  4,4'-Difluorodiphenyl sulfone commercially available from Aldrich (99% grade, 99.32% measured) or Marshallton (99.92% pure by GC).

  Diphenyl sulfone (polymer grade) commercially available from Proviron (99.8% pure).

Potassium carbonate with d ₉₀ <45 μm, commercially available from Armand products.

  Lithium chloride (99 +%, ACS grade) commercially available from Acros.

KetaSpire® KT-820 NT, PEEK (polyetheretherketone) fines (maximum particle size defined by 100% passage through a 100 mesh screen, as well as ASTM D3835 in the range 0.38-0.50 kPa-s. Using 400 ° C. and 1000 s ⁻¹ melt viscosity); commercially available from SOLVAY SPECIALTY POLYMERS USA, LLC.

General procedure for the preparation of t-PAES polymers-Example 1 and Example 2
Stirrer, N ₂ inlet tube, a Claisen adapter with a thermocouple digs into the reaction medium, and in a four-necked reaction flask of 500mL Dean Stark trap was attached with a condenser and drying ice trap, 89.25G Of diphenyl sulfone, 28.853 g of a specific type of 1,1 ′: 4 ′, 1 ″ -terphenyl-4,4 ″ -diol and 27.968 g of 4,4′-difluorodiphenylsulfone (38 0.9% total monomer% and 1.000 equivalent of dihalo (BB) / diol molar ratio) were introduced. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (less than 10 ppm O ₂ ). The reaction mixture was then placed under a constant nitrogen purge (60 mL / min). The reaction mixture was slowly heated to 220 ° C. At 220 ° C., 15.354 g of K ₂ CO ₃ was added to the reaction mixture via a powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 320 ° C. at 1 ° C./min. After 13 minutes at 320 ° C., 1.119 g of 4,4′-difluorodiphenyl sulfone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 2 minutes, 4.663 g of lithium chloride was added to the reaction mixture. After 2 minutes, another 0.280 g of 4,4′-difluorodiphenyl sulfone was added to the reactor and the reaction mixture was maintained at temperature for 5 minutes. The reactor contents were then poured from the reactor into a stainless steel pan and allowed to cool. The solid was crushed and ground in an attrition mill through a 2 mm screen. Diphenylsulfone and salt were extracted from this mixture with acetone, then water at a pH between 1 and 12, then acetone. The powder was then removed from the reactor and dried under vacuum at 120 ° C. for 12 hours to obtain 44 g of a light brown powder. The powder was then further pulverized in a laboratory scale pulverizer to obtain a fine powder having an average particle size of approximately 100 μm.

  Examples 1 and 2 were prepared according to this general procedure. Except for Example 2, instead of after 13 minutes at 320 ° C., after 27 minutes at 320 ° C., 1.119 g of 4,4′-difluorodiphenyl sulfone was added to the reaction mixture while a nitrogen purge was applied in the reactor. Maintained.

The molecular weight of the final t-PAES polymer was measured by GPC as detailed below and in the case of Example 1 it was found that M _n was 39,000 g / mol and Mw was 112,500 g / mol. found to be moles; in the case of example 2, _{M n} is despite to be 47,925G / mol, Mw was found to be 97,036G / mol, 29% crystallinity.

General description of the molding process of (t-PAES) polymer material-Example 1 and Example 2
The t-PAES polymer (Example 1 or Example 2) or PEEK fine powder polymer (Comparative Example 3) was 4 inches × 4 using a Fontijne programmable compression machine according to the compression molding protocol as shown in Table 1. Compression molded into inch x 0.125 inch plaques. Next, the compression molded plaques of Example 1 and Comparative Example 3 were machined into Type V ASTM tensile test pieces and 0.5 inch wide bend test pieces, and these test pieces were simulated oil field conditions, ie, detailed below. Before and after exposure to rapid gas depressurization as in a wellbore environment of an oil field as described in Section II, subjected to a tensile test according to ASTM method D638 and a bending test according to ASTM method D790 (see Table 3).

  The compression molded plaque of Example 2 was machined into 2 inch x 0.5 inch x 0.125 inch specimens. The test specimens were immersed in concentrated sulfuric acid at room temperature, and their weight and appearance were examined every 24 hours. The results after 240 hours of immersion are summarized in Table 2.

  The results in Table 2 clearly demonstrate the excellent resistance of the inventive t-PAES polymer to oxidative acids.

The following characteristic evaluation carried out on the materials of the examples is shown below.
Molecular weight measurement by GPC method GPC conditions:
Pump: 515 HPLC pump from Waters Detector: UV 1050 series from HP Software: Empower Pro from Waters
Injector: Waters 717 Plus Auto Sampler flow rate: 0.5 ml / min UV detection: 270 nm
Column temperature: 40 ° C
Column: Agilent 2x PL Gel Mixed D, 5 micron, 300 mm x 7.5 mm 5 micron Injection: 20 μl Run time: 60 minutes Eluent: N-methyl- with 0.1 molar lithium bromide (Fisher make) 2-Pyrrolidone (Sigma-Aldrich, Chromasolv Plus for HPLC> 99%). The mobile phase must be stored under nitrogen or an inert environment.
Calibration standard: A polystyrene standard product number PL2010-0300 from Agilent was used for calibration. Each vial has four narrow polydisperse polystyrene standards (a total of 11 standards used to establish a calibration curve, 371100, 238700, 91800, 46500, 24600, 10110, 4910, 2590, 1570, 780). In.
Standard concentration: 1 ml of mobile phase was added to each vial prior to GPC injection for calibration.
Calibration curve: 1) Type: Relative narrow standard calibration 2) Fitting: cubic regression integration and calculation: Emperor Pro GPC software from Waters is used to obtain data, calibration and molecular weight calculations. The peak integration start and end points are manually determined from significant differences across the baseline.

  Sample preparation: 25 mg of (t-PAES) polymer was dissolved in 10 ml of 4-chlorophenol after heating at 170-200 ° C. A small amount (0.2-0.4 ml) of the obtained solution was diluted with 4 ml of N-methyl-2-pyrrolidone. The resulting solution was passed through a GPC column according to the GPC conditions described above.

Oil Field Simulated Condition Rapid Gas Decompression Test A rapid gas decompression (RGD) test was first performed on the bending bar samples of Example 1 and Comparative Example 3. This test evaluates the ability of plastic materials to withstand rapid gas decompression in an oil well bore environment. To perform this test, the bend-formed specimens from Example 1 and Comparative Example 3 were first placed in a pressure vessel, the vessel was sealed and heated to 175 ° C. A 90/10 by weight methane / CO ₂ mixture was then introduced into the pressure vessel and the pressure in the vessel was increased to 1000 bar (14500 psi). After maintaining one week at these test pressures and temperatures, the pressure was automatically released from the container at a controlled rate of 70 bar / min. The pressure and temperature profile curves for this test are shown in FIG. Following exposure, the specimens of Example 1 and Comparative Example 3 were removed from the pressure vessel and subjected to weight and volume change measurements and bending property tests. Measurements are made on 5 replicates for each material and the results as shown in Table 3 are the average of 5 replicates. The appearance of the exposed specimen was visually observed and recorded in Table 3.

Hot oil exposure test The hot oil exposure test was performed using ASTM tensile test specimens from Example 1 and Comparative Example 3 as described above. The hot oil exposure test was initiated with vapor pressure prevailing in a pressure cell equipped with an external heater band, thermocouple and calibration pressure sensor. Pressure and temperature were recorded by a PC running dedicated software. Specimens were exposed in a high pressure cell at a temperature of 270 ° C. and vapor pressure for a period of 3 days, after which the specimens were removed and measured for weight change and dimensional change, and then returned for another 3 days exposure time under the same conditions. . At the end of the 3rd day of the second exposure, the specimen is removed as the final time, weight and dimensional changes are measured, recorded, and a tensile test is performed on the exposed specimen, resulting in high pressure and high temperature oil exposure results. As to whether there was any grade degradation in mechanical performance. The results of weight and volume changes before and after exposure and the tensile properties are recorded in Table 4.

Claims (14)

Oil comprising at least one part made from a poly (aryl ether sulfone) polymer material (hereinafter (t-PAES) polymer material) comprising at least one poly (aryl ether sulfone) polymer [(t-PAES) polymer] And a gas recovery article, wherein the (t-PAES) polymer has the formula (S _t ):
^{_{-E-Ar 1 -SO 2 - [}} Ar 2 - (T-Ar 3) n -SO 2] m -Ar 4 - Formula (St)
[Where:
-N and m are equal to or different from each other and are independently zero or an integer from 1 to 5;
Each of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ that are equal or different from each other and each occurrence is an aromatic moiety;
-T is a bond, or a one or two or more may also be divalent groups which contain a hetero atom; preferably T is a _{bond, -CH 2 -, - C (} O) -, - C (CH 3 ) ₂ −, —C (CF ₃ ) ₂ —, —C (═CCl ₂ ) —, —C (CH ₃ ) (CH ₂ CH ₂ COOH) —, and the formula:
Selected from the group consisting of
-E is the formula (E _t ):
(Where
Each of -R 'is equal to or different from each other, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, Selected from the group consisting of alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines and quaternary ammoniums, j ′ is zero or an integer from 1 to 4)
belongs to]
Oil and gas recovery articles comprising more than 50 mol% of repeating units (R _t ). The repeating unit (R _t ) is represented by the following formula (S _t -1) to formula (S _t -4):
(Where
Each of -R 'is equal to or different from each other, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, Selected from the group consisting of alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines and quaternary ammonium;
-J 'is zero or an integer from 1 to 4,
-T is a bond, or a one or two or more may also be divalent groups which contain a hetero atom; preferably T is a _{bond, -CH 2 -, - C (} O) -, - C (CH 3 ) ₂ −, —C (CF ₃ ) ₂ —, —C (═CCl ₂ ) —, —C (CH ₃ ) (CH ₂ CH ₂ COOH) —, and the formula:
Selected from the group consisting of
The oil and gas recovery article of claim 1 selected from the group consisting of:   The oil and gas recovery article according to claim 1 or 2, wherein the (t-PAES) polymer material further comprises one or more additional feedstock (I) that is different from the (t-PAES) polymer.   4. The oil and gas recovery article according to any one of claims 1 to 3, wherein the (t-PAES) polymeric material further comprises at least one reinforcing filler.   The oil and gas recovery article is a drilling system, drilling rig, compressor system, pumping system, motor system, sensor, control system, liner hanger, packer system, pipe system, valve system, tubing system, or casing system; The oil and gas recovery article according to any one of claims 1 to 4.   Oil and gas recovery article according to claim 6, wherein the pipe system is a pipe, flexible riser, pipe-in pipe, pipe liner, underwater jumper, spool or supply pipeline, preferably a pipe, flexible riser or pipe liner.   The oil and gas recovery article according to any one of claims 1 to 5, wherein the portion is a seal, a fastener, a cable, an electrical connector, or an oil and gas recovery housing.   8. Oil and gas recovery according to claim 7, wherein the part is a seal suitable for use in drill bits, motor systems, reservoir sensors, stimulation and flow control systems, pump systems, packers, liner hangers, tubing, casings and the like. Goods.   9. Oil and gas recovery article according to claim 8, wherein the seal is a seal ring, preferably a backup seal ring.   6. Oil and gas recovery article according to any one of the preceding claims, wherein the part is a coating, preferably a wire coating.   11. A portion of an oil and gas recovery article according to any one of claims 1 to 10, or a method for the manufacture of an oil and gas recovery article, comprising steps of injection molding, extrusion or other shaping technique.   12. A part of an oil and gas recovery article according to claim 11 or a method for the manufacture of an oil and gas recovery article comprising the steps of injection molding and solidification of the (t-PAES) polymer material.   12. A part of oil and gas recovery article according to any one of claims 1 to 11, or a method for the production of oil and gas recovery article, comprising a step of coating, preferably extrusion coating. A method for recovering oil and / or gas from a subterranean formation comprising using the oil and gas recovery article according to any one of claims 1-11.
(A) drilling at least one borehole to explore or develop an oil and / or gas reservoir in the underground using at least one oil and gas recovery article as defined above;
(B) finishing at least one well using at least one oil and gas recovery article as defined above;
(C) A method comprising at least one operation selected from the group consisting of transferring oil and / or gas from an oil and / or gas reservoir in the underground to the ground surface.