A crosslinking composition for forming a crosslinked organic polymer, an organic polymer composition, a method for forming the same, and a molded article produced therefrom.

Abstract

To provide crosslinked polymers [Solution] The present invention provides a crosslinking compound having a structure described herein for a crosslinked organic polymer. Furthermore, the polymer composition comprises the crosslinking compound and the organic polymer, and in some embodiments, the composition further comprises a crosslinking reaction additive for controlling the crosslinking reaction rate. In alternative embodiments, the present invention provides a crosslinking composition comprising a crosslinking compound and a crosslinking reaction additive that can form a reactive intermediate oligomer for crosslinking the organic polymer. Furthermore, methods for crosslinking an organic polymer, the organic polymer formed thereby, and molded articles formed from the crosslinked organic polymer are provided. In addition, methods for forming a high glass transition temperature elastomer material, as well as methods for forming a material that is resistant to extrusion and creep are provided.

Description

[Technical Field]

[0001] Cross-reference of related applications

[0002] This U.S. Patent Nonprovisional Application asserts, under § 119(e), the benefits of U.S. Patent Provisional Application No. 62 / 730,000, filed on September 12, 2019, entitled "Cross-Linking Compositions for Forming Cross-Linked Organic Polymers, Organic Polymer Compositions, Methods of Forming the Same," and further claims, under § 119(e), the benefits of "Crosslinkable Aromatic Polymer Compositions for Use," filed on September 11, 2019. in Additive Manufacturing Processes and We assert the interests of U.S. Provisional Patent Application No. 62 / 729,999, entitled “Methods for Forming the Same,” pursuant to § 119(e) of the U.S. Patent Act, and the entirety of these disclosures is incorporated herein by reference.

[0003] Background of the Invention Field of Invention The present invention relates to crosslinked compositions and mixtures for forming crosslinked high glass transition polymer systems. Furthermore, the present invention relates to methods for producing such polymers and methods for controlling the crosslinking reaction rate of crosslinked compounds in such compositions that form high glass transition temperature organic polymers that can be used to form seals and other wear-resistant components for use, for example, in underground tooling applications. The present invention further relates to the use of such crosslinked organic polymer materials as a method for improving the extrusion resistance and creep resistance of components in high-temperature end applications, such as in high-temperature sealing applications, where conventional and / or high-purity elastomers lose performance due to polymer degradation. [Background technology]

[0004] Explanation of related technologies High glass transition temperature polymers are referred to herein as "high T g It is also called a polymer and is useful for several high-temperature applications. g Modifying organic polymers generally improves their high-temperature performance, strength, and chemical resistance compared to unmodified organic polymers, making them suitable for use in fabricated parts and products required in extreme temperature environments.

[0005] Crosslinking has become widely recognized as a method for modifying high-temperature polymeric materials. Several inventions have aimed to improve the high-temperature performance of organic polymers by using crosslinking within polymers, such as by crosslinking itself, grafting crosslinking compounds into polymers, or incorporating crosslinking compounds into polymers through blends.

[0006] U.S. Patent No. 5,874,516, vested in the applicant of this application and incorporated herein by reference in the relevant portion, reveals a poly(arylene ether) polymer that is thermally stable, has a low dielectric constant, low hygroscopicity and low moisture generation. The polymer further has a structure that can be crosslinked by itself or can be crosslinked using a crosslinking agent.

[0007] U.S. Patent No. 6,060,170, vested in the applicant of this application and incorporated herein by reference in the relevant portion, describes the use of a poly(arylene ether) polymer composition having aromatic groups grafted onto a polymer backbone, wherein the grafts are suitable for temperatures of about 200°C to about 450°C. This patent discloses the ability to crosslink polymers in a temperature range of °C. The patent also discloses dissolving a polymer in a suitable solvent for grafting crosslinking groups. Such necessary process steps can sometimes be difficult or impractical for certain types of polymers or polymeric structures, such as polyether ether ketones (PEEKs).

[0008] U.S. Patent No. 8,502,401, vested in the applicant of this application and incorporated herein by reference in the relevant portion, describes a per(phenylethynyl)arene polymer that provides a polymeric network grafted and crosslinked onto a second polymer.

[0009] Attempts have also been made in the past to control the formation of crosslinks along high-glass transition polymers in order to obtain desired mechanical properties and high-temperature polymers. The applicant's U.S. Patent No. 5,658,994, incorporated herein by reference in the relevant section, describes the use of poly(arylene ether) in a low-dielectric intermediate layer, which can be crosslinked, for example, by crosslinking the polymer itself, by exposure to temperatures above about 350°C, or alternatively by the use of a crosslinking agent. In this patent, and also cited in U.S. Patent No. 5,874,516, crosslinking occurs at the ends of the polymer backbone using known end-canceling agents such as phenylethynyl, benzocyclobutene, ethynyl, and nitrile. The degree of crosslinking may be limited, resulting in lower glass transition temperatures, lower chemical resistance, and lower tensile strength.

[0010] U.S. Patent No. 9,006,353 of the applicant of this application is also incorporated herein by reference in the relevant portion and discloses a crosslinking compound that is blended with an uncrosslinked polymer to achieve a crosslinked organic polymer having a higher glass transition temperature for use in extreme conditions such as underground tooling applications.

[0011] Such crosslinking agents may be effective, but controlling the rate and degree of crosslinking can be difficult. Crosslinked organic polymers having aromatic groups in their backbone, such as crosslinked polyether ether ketone (PEEK) crosslinked polyarylene ether polymers, can be difficult to control even when prepared using reagents to control crosslinking as described herein, especially at high temperatures (above approximately 270°C). gIt is an amorphous polymer that functions well at high temperatures (having the following properties). Crosslinking adds high chemical resistance to the base polymer against high temperatures. Crosslinking can be performed using the applicant's techniques, as specified above and described in the patents and published patent applications described herein. During molding, the controlled crosslinked polymer is subjected to temperatures of approximately 250°C (or the T of the material). g It works well at temperatures slightly lower than that. However, as the molding temperature rises, the reaction can accelerate so that complete curing can be achieved in less than a minute. However, the cycle time for injection molded parts such as tubes, rods, or electrical connectors is generally 3 to 5 minutes or longer. Complete curing in less than a minute can hinder the usefulness of conventional molding techniques such as injection molding or extrusion when forming molded parts.

[0012] Prior art attempts to delay or suppress reactions, as well as mild crosslinking reactions using compounds and their reactions, are known. (Vanderbilt Rubber Handbook, 13th ed., 1990, p.281) reference.

[0013] Furthermore, in U.S. Patent No. 9,109,080, incorporated herein by reference in the relevant portion, the applicant previously disclosed crosslinking compositions comprising crosslinking compounds and crosslinking reaction additives that improve the ability to control and suppress such reactions and to process such polymers more easily using conventional molding techniques. However, some crosslinking compounds are more difficult and / or expensive to produce than others and require the use of extreme reaction conditions and harsh chemical reagents. Among these crosslinking compounds are 9-fluorinated as a ketone unit. Based on Lennon, the types of crosslinking compounds that can be manufactured are relatively limited, the crosslinking compounds have high melting points, and the use of these crosslinking compounds may be limited to similar high-temperature processed polymers.

[0014] Therefore, it is desirable to use a variety of crosslinking compounds that are at least as effective as the crosslinking compounds previously identified by the applicant, can be manufactured more easily and at less cost using less harsh chemicals and milder reaction conditions. Crosslinking compounds can also enable crosslinked polymers over a wider temperature range. Such new crosslinking compounds can be used in elastomer applications as a substitute for elastomers such as fluorine-containing elastomers, or in high-temperature end applications with respect to elastomer use.

[0015] Fluorine-containing elastomers, particularly perfluoroelastomers (FFKMs) containing tetrafluoroethylene (TFE) and other fluorinated monomer units, are well known and used in end applications where materials exhibiting excellent chemical resistance, solvent resistance, and heat resistance are required. They are widely used in sealing and other products intended for use in harsh environments. Furthermore, FFKMs are used in end applications where high purity is required in addition to chemical resistance. As technology advances, the properties required even for such highly resistant compounds continue to become more stringent. In the fields of aerospace, underground oil extraction, semiconductor manufacturing, chemical manufacturing, and pharmaceuticals, sealing and other elastomer properties continue to demand the ability to function under increasingly harsh chemical environments, including exposure to high temperatures of 300°C or above. The ability of such materials to withstand high-temperature environments is becoming increasingly important.

[0016] FFKM offers excellent chemical and plasma resistance, but in its unfilled state, its mechanical properties are typically weaker. Thus, to achieve satisfactory compression set resistance and mechanical properties, it is generally known in the art to include fillers or other reinforcing systems. The goal in the art is to find ways to blend, modify, or fill such materials to form molded parts that are suitable for high-temperature end applications, can withstand deformation, and can withstand constantly increasing harsh conditions. FFKM materials are typically prepared from perfluoromonomers containing at least one perfluorocurable site monomer. The monomers polymerize to form a curable perfluoropolymer with curable sites, which are intended to be crosslinked in reaction with a curing agent or curing agent. Upon curing (crosslinking), the base polymer material becomes essentially an elastomer and exhibits elastomeric properties.

[0017] Typical fillers used in semiconductor and other industries to enhance mechanical properties without compromising chemical and / or plasma resistance include carbon black, silica, alumina, TFE-based fluoropolymers, barium sulfate, and other polymers and plastics. Blends of one or more FFKM curable polymers are sometimes made to achieve a variety of properties in attempts to improve such materials to address the challenge of higher heat resistance, chemical resistance, and plasma resistance requirements for various end applications without sacrificing mechanical and sealing properties.

[0018] The use of fluoropolymer fillers in such compositions can sometimes lead to disadvantages, particularly in end applications at high temperatures (e.g., >300°C), resulting in relatively high compression set. Moldability and bonding properties can also be limited by the use of such fluoropolymer fillers.

[0019] To provide base FFKM compounds with improved thermal properties, various polymers have also been developed using unique curing systems. One example of this is U.S. Patent No. 6,855,774. The formed crosslinks are described as contributing to increased heat resistance. U.S. Patent No. 6,878,778 further teaches a curing agent which is described as contributing to the resulting final material having excellent chemical resistance and mechanical strength as well as heat resistance at high temperatures.

[0020] Blended FFKMs have also been developed to achieve unique properties. FFKMs such as those formed from U.S. Patents 6,855,774 and 6,878,778, as well as other FFKMs, are similarly blended. U.S. Patent 8,367,776 describes a composition comprising such polymers and one or more additional FFKMs, in which two of the FFKM compounds in the composition differ by about 5 to about 25 mol percent in terms of perfluoroalkyl vinyl ether (PAVE) monomer content. Such blends are described as providing the ability to form compositions that can function well without the use of fluoropolymer fillers, serving as an alternative to such filled materials and, in some cases, providing an improvement. Such blends offer crack resistance in the presence of harsh chemicals, as well as good heat and plasma resistance.

[0021] U.S. Patent No. 9,018,309 describes a blend of two or more FFKMs, one of which is a curable perfluoropolymer with a high TFE content (as in U.S. Patent No. 8,367,776), and the other is a fluoropolymer incorporated into a matrix of a second curable perfluoropolymer. The combined material provides improved high-temperature properties. Such materials are state-of-the-art technology for high-temperature elastomers and demanding environments where chemical and / or plasma resistance is required.

[0022] While technology continues to strive to improve the mechanical and compression set performance of FFKM in high temperatures and increasingly harsh environments, while maintaining the advantageous chemical and / or plasma resistance of these materials by levels of chemical purity and inertness, performance issues remain that will become increasingly important in the art as end users continue to push the limits of operating conditions for such materials. As temperatures rise, FFKM decomposes thermally, limiting its usable range. Modifications of additives and various blends and / or curing agents are attempting to push the range, but limitations still exist.

[0023] While other polymers are well-known for high-temperature applications, they are not always suitable for all harsh environments where a combination of mechanical and elastomeric properties is required. Aromatic polymers such as polyarylenes are known to possess a thermally stable backbone, but until recently, they were generally not suitable for end-use elastomers. Attempts have been made in the art to use crosslinked thermally stable polymers that are non-elastomeric at room temperature, and then to use them at operating temperatures above their glass transition temperature.

[0024] International Publication No. 2011 / 071619 discloses the use of a high-temperature sealing element incorporating polyether ether ketone (PEEK) with N-Rx-N crosslinking groups linked by CN bonds, in order to avoid degradation during underground use.

[0025] Similarly, JL Hendrick et al., "Elastomeric Behavior of Cross-linked Poly(aryl ether ketone)s at Elevated Temperatures," Polymer, Vol. 33, No. 23, pp. 5094-5097 (1992). PEEK is linked to malean anhydride via an oligomeric terminal group. Cross-linked by acid and its T gIt forms PEEK, which exhibits elastomeric properties at higher temperatures. However, until recently, such systems had not yet achieved the desired high-temperature and / or hydrolysis stability to be useful as an alternative to FFKM and in high-temperature end applications requiring the right balance of mechanical properties and elastomeric properties.

[0026] U.S. Patent Application Publication No. 2013 / 0012635 describes shape memory materials and supplies. A thermoplastic material is disclosed, and the thermoplastic material has T g It is formed by heating the shape memory polymer upwards, shaping the polymer, and then T g By cooling to below the temperature, the shape is fixed onto the product. In use, the product thus molded is its T g Further heating restores the first molded shape. The polymers suggested for use are those that have thermal stability above 200°C, which may be cured in the presence or absence of oxygen. Crosslinking agents such as sulfur, silica, quinone, peroxy compounds, metal peroxides, metal oxides, and combinations thereof can be used for crosslinking with the shape memory polymer.

[0027] Some prior art systems attempting such high-temperature elastomer final products with crosslinking employ complex chemical synthesis of polymers, or polymers containing specific functional groups. This approach limits the ability to customize the crosslinking density because the polymer is fixed during the synthesis stage. Greater flexibility would allow for the customization of the final material for various applications.

[0028] FFKM is not known as a very strong elastomer. However, it is resistant, and filler systems are used in attempts to improve its shortcomings due to thermal stability. If thermal stability can be improved and better mechanical properties are achieved, a material that can meet the ever-increasing needs in high-temperature and demanding environments is available in the art. Further products can be designed, although this is not possible at present due to the limitations of available materials.

[0029] The applicant of this application, U.S. Patent No. 9,109,075, also incorporated herein by reference in relevant portions, discloses crosslinked organic polymers for high-temperature end-use. While crosslinked organic polymers for high-temperature end-use are provided, the crosslinking compounds used in such crosslinked organic polymers may be difficult and / or expensive to manufacture. It is desirable to provide a variety of crosslinking compounds that are not so expensive and are easily manufactured for use in the manufacture of polymers for high-temperature end-use.

[0030] Sealing components and other wear-resistant materials can be used in extremely harsh and demanding environments. Their wear resistance and mechanical properties are crucial for applicability and service life. For example, sealing components are typically formed from elastomer materials located in the gland. In one application, annular seals may be fitted within the gland and installed to seal gaps between surfaces. For example, a seal may be installed around an axis fitted within a cavity, where the cavity can be configured to receive the seal into the gland. In many cases, seals are not installed independently but are part of a seal assembly. Such assemblies may include backing rings and other components. Seals and seal assemblies are usually constructed to support the main sealing element and are generally formed from elastomer materials to prevent the material from overflowing into the gland and into the space or gap between sealing surfaces.

[0031] When the operating temperature is high, a pure elastomeric seal may not be able to provide sufficient sealing force to prevent leakage and / or may bulge into the gap between the sealing surfaces, e.g., bulge out to the shaft and the seal. Under such conditions, a thermoplastic material having a higher shear strength may be used to separate the soft elastomeric component from the gap between the sealing surfaces to assist in resisting bulging. Combinations of harder and softer materials are also sometimes used, such that the softer material (e.g., polytetrafluoroethylene (PTFE), or other fluoropolymer materials, etc.) is prevented from bulging into the gap by the more rigid thermoplastic anti-bulge component. Such materials are used in both one-way and two-way sealing assemblies.

[0032] Materials used as anti-bulge components include polyether ether ketone (PEEK) and similar polyketones. The continuous service temperature of such materials, including commercially available polyaryl ketones such as Victrex® polyarylene, ranges from about 240 °C to about 260 °C.

[0033] In use at high temperatures, the polyketones become significantly higher than their glass transition temperatures. For example, PEEK is semi-crystalline and has a T g of 143 °C. Other polyketones such as Victrex® PEK and PEKEKK have glass transition temperatures of 152 °C and 162 °C, respectively.

[0034] Since semi-crystalline materials are used above their glass transition temperatures, they tend to exhibit a decrease in mechanical properties during use, and the performance correspondingly decreases. With respect to FIGS. 2 and 3, this effect can be seen when the PEEK ring is loaded below and above its glass transition temperature, respectively, and a significant difference in anti-bulge resistance can be seen. FIG. 3 shows a 60% increase in bulge at 50% lower pressure for the same loading period.

[0035] Furthermore, such overhang issues are problematic in the field of electrical connectors. Such connectors are used to relay electrical signals from sensors to electronics in underground oil exploration tools. They also function as bulkhead seals, being the last line of defense against damage to the electronics of the oil exploration tool in the event of a sudden tool failure. Such seals must be able to withstand high temperatures and high pressures for extended periods. Unfortunately, many underground oilfield products use various commercially available polyketones. g Used at or above a certain temperature, severe overhang can occur as a result. Often, such overhang leads to failure of the component as a seal, either allowing moisture to leak through the seal or causing the component to deform and no longer function properly mechanically. An example of this behavior can be seen in Figure 4, which shows overhang in an electrical connector.

[0036] Attempts have been made to enhance the properties of PEEK. As discussed earlier, crosslinking has been widely recognized as one method of modifying high-temperature polymeric materials. Several inventions have aimed to improve the high-temperature performance of organic polymers by using crosslinking within the polymer, by crosslinking itself, by grafting crosslinking compounds into the polymer, or by incorporating crosslinking compounds into the polymer through blends, etc.

[0037] U.S. Patent No. 5,173,542 discloses the use of bistriazene compounds for crosslinked polyimides, polyarylene ketones, polyaryl ethersulfones, polyquinolines, polyquinoxalines, and non-aromatic fluoropolymers. The resulting crosslinked polymers are useful as intermediate layer insulators in multilayer integrated circuits. The challenges encountered in the art discussed by the patent involve controlling the crosslinking process of aromatic polymers to enhance their properties. It proposes bistriazene crosslinked structures and methods that enhance chemical resistance and reduce cracking so that useful intermediate layer materials can be formed.

[0038] Other attempts to crosslink polymers to enhance their high-temperature properties have encountered difficulties regarding the thermal stability of the polymers. Other problems arise in terms of controlling the rate and degree of crosslinking.

[0039] U.S. Patent No. 5,874,516, vested in the applicant of this application and incorporated herein by reference in the relevant portion, demonstrates that a thermally stable polyarylene ether polymer has low dielectric constant, low hygroscopicity, and low moisture-releasing properties. The polymer further has a structure that can be crosslinked by itself and can be crosslinked using a crosslinking agent.

[0040] Further patents, U.S. Patent No. 5,658,994, discuss polyarylene ether polymers that can be crosslinked by themselves or by the use of crosslinking agents, for example, by exposure to temperatures higher than approximately 350°C. The patent also describes the end-binding of polymers using known end-binding agents such as phenylethynyl, benzocyclobutene, ethynyl, and nitrile. Because the limited crosslinking is present at the ends of the chain, the associated properties, namely glass transition temperature, chemical resistance, and mechanical properties, are not sufficiently enhanced for all high-temperature applications.

[0041] Further developments in improving the properties of polyarylene ether polymers are described in U.S. Patent No. 8,502,401, which describes the use of per(phenylethynyl)arene as an additive for polyarylene ethers, polyimides, polyureas, polyurethanes, and polysulfones. The patent discusses the formation of a semi-interpenetrating polymer network structure between two polymers to improve their properties.

[0042] Applicant's U.S. Patent No. 9,006,353 concerns structure: [ka] This describes compositions having crosslinked compounds of [wherein R is OH, NH2, halide, ester, amine, ether, or amide, x is 2-6, and A is an arene moiety having a molecular weight of less than about 10,000 g / mol]. When reacted with aromatic polymers such as polyarylene ketones, it forms a heat-stable, crosslinked polymer. This technique gives crosslinking of polymers that are difficult to crosslink, and they are heat-stable to temperatures above 260°C, and even 400°C or higher, depending on the polymer thus modified (i.e., polysulfone, polyimide, polyamide, polyether ketone and other polyarylene ketones, polyurea, polyurethane, polyphthalamide, polyamideimide, aramid, and polybenzimidazole).

[0043] Polyimides and polyamide-imide copolymers have glass transition temperatures of approximately 260°C or higher, but they tend to become unusable in strong acidic, basic, or aqueous environments because they are easily damaged by chemical attack. Consequently, although their working temperatures are more attractive, their chemical resistance limits their usefulness in sealing applications where the liquid medium is aqueous or otherwise harmful to the material. For example, the applicant's testing of polyimides showed a loss of approximately 80% of their properties after aging in steam at 200°C for 3 days, using ASTM-D790 to test the flexural modulus.

[0044] All aromatic polysulfones, such as polyethersulfone (PES) and polyphenylsulfone (PPSU), may be used in such end applications, but their amorphous nature presents a problem: they are susceptible to stress cracking in the presence of strong acids and bases. Due to the possibility of amorphous polymers flowing at temperatures close to their glass transition temperature over time, the continuous use temperature is typically set about 30°C to 40°C below the glass transition temperature. Thus, for continuous use of polysulfone (PSU), it is recommended to set the temperature to 180°C, given that the glass transition temperature is approximately 220°C.

[0045] Other problems encountered in more demanding end uses, such as exposure to harsh chemicals, water, and / or vapors, include issues related to plasticizer effects, which occur when polymers absorb chemicals that can increase the motion of molecular chains and lower the glass transition temperature from their standard state in an unswelled polymer.

[0046] A further issue relates to creep. When a polymer operates above its glass transition temperature, creep is a limiting factor for a sealing component that can deform under harsh conditions. Thus, to improve mechanical properties, prevent creep, and resist extrusion, most high-temperature polymers are filled for use as lining rings or molded components during use. The disadvantage of using fillers is that they typically significantly reduce ductility. For example, unfilled PEEK has about 40% tensile elongation, while 30% carbon-filled PEEK has only 1.7% tensile elongation at fracture. Thus, the material becomes more brittle from the reinforcing filler, and this brittleness can lead to partial cracking under long-term loading. The use of fillers also causes differences in the coefficient of thermal expansion in the mold-to-transverse direction of the molded part. This can also cause considerable in-molding stress. Even when not under significant load, the end result is cracking over time due to creep rupture. U.S. Patent No. 9,127,138 and U.S. Patent Application Publication No. 2015 / 0544688, borne by the applicant and incorporated herein by reference in relevant portions, relate to sealing components formed from organic aromatic polymers and crosslinked compounds, providing sealing components that are extrusion-resistant and creep-resistant. However, the crosslinked compounds therein can be difficult and expensive to manufacture. It is desirable to use crosslinked compounds that can be manufactured more easily under milder reaction conditions and to form extrusion-resistant and creep-resistant sealing components with less use of harsh reagents, so that the crosslinked compounds can be manufactured at a lower cost. Thus, while the applicant has developed a novel method using previously crosslinked aromatic polymers, there is a need in the art for alternative crosslinking compounds that offer an alternative method that is easier to use and more cost-effective, but at least as effective as those in the applicant's prior patents. Such alternative crosslinking compounds must still function effectively as sealing components, seal connectors, and similar parts. Maintaining good mechanical properties, resisting the extrusion of seal or connector material into gaps between two surfaces to be sealed or along pins, resisting creep when used without becoming brittle or significantly losing its ductility, the crosslinking compounds must be suitable for operation at high operating temperatures associated with oil fields and other harsh conditions and industrial applications. [Prior art documents] [Patent Documents]

[0047] [Patent Document 1] U.S. Patent No. 5,874,516 [Patent Document 2] U.S. Patent No. 6,060,170 [Patent Document 3] U.S. Patent No. 8,502,401 [Patent Document 4] U.S. Patent No. 5,658,994 [Patent Document 5] U.S. Patent No. 9,006,353 [Patent Document 6] U.S. Patent No. 9,109,080 [Patent Document 7] U.S. Patent No. 6,855,774 [Patent Document 8] U.S. Patent No. 6,878,778 [Patent Document 9] U.S. Patent No. 8,367,776 [Patent Document 10] U.S. Patent No. 9,018,309 [Patent Document 11] International Publication No. 2011 / 071619 [Patent Document 12] U.S. Patent Application Publication No. 2013 / 0012635 [Patent Document 13] U.S. Patent No. 9,109,075 [Patent Document 14] U.S. Patent No. 5,173,542 [Patent Document 15] U.S. Patent No. 9,127,138 [Patent Document 16] U.S. Patent Application Publication No. 2015 / 0544688 [Non-patent literature]

[0048] [Non-Patent Document 1] Vanderbilt Rubber Handbook, 13th ed., 1990, p.281 [Non-Patent Document 2] JL Hendrick et al., "Elastomeric Behavior of Cross-linked Poly(aryl ether ketone)s at Elevated Temperatures," Polymer, Vol. 33, No. 23, pp. 5094-5097 (1992) [Overview of the project] [Means for solving the problem]

[0049] The present invention relates to a crosslinking composition for crosslinking organic polymers, wherein the formula is as follows: [ka] [In the formula, Q is a bond, A is an alkyl, aryl, or arene moiety having a molecular weight of less than approximately 10,000 g / mol, and R 1 , R 2 and R 3 Each of them has a molecular weight of less than approximately 10,000 g / mol, R 1, R 2 and R 3 The present invention provides a crosslinked composition comprising a crosslinked compound having a structure in which one or more of the following are selected from the group consisting of hydrogen, hydroxyl (-OH), amine (-NH2), halide, ether, ester, amide, aryl, arene, or branched or linear saturated or unsaturated alkyl groups having 1 to about 6 carbon atoms, m is 0 to 2, n is 0 to 2, m+n is greater than 0 or equal to 0 and less than 2 or equal to 2, Z is selected from the group consisting of oxygen, sulfur, nitrogen, and branched or linear saturated or unsaturated alkyl groups having 1 to about 6 carbon atoms, and x is about 1.0 to about 6.0.

[0050] In some embodiments, the crosslinking composition may comprise a blend of one or more crosslinking compounds selected from formulas (I), (II), and (III). Furthermore, in other embodiments, the crosslinking composition may comprise at least one crosslinking compound selected from formulas (I), (II), and (III), and may also comprise at least one additional crosslinking compound, such as a crosslinking compound of the type disclosed in U.S. Patent No. 9,006,353. One or more crosslinking A blend of compounds may be used, but a single crosslinking compound is preferred.

[0051] The crosslinked compound in the composition described above may have the structure of formula (I), and the following [ka] You may choose from the group consisting of the following:

[0052] The crosslinked compound in the composition described above may have the structure of formula (II), and the following [ka] [ka] It is selected from the group consisting of the following.

[0053] The crosslinked compounds in the compositions described above also have the structure of formula (III), and further as follows: [ka] It may have a structure based on the following.

[0054] The arene, alkyl, or aryl moiety A of the crosslinked compound according to formula (I) or (II) described above preferably has a molecular weight of about 1,000 g / mol to about 9,000 g / mol, more preferably about 2,000 g / mol to about 7,000 g / mol.

[0055] In another embodiment, the present invention includes an organic polymer composition for use in forming a crosslinked organic polymer, comprising an organic polymer and at least one crosslinked compound having a structure selected from formulas (I), (II), and (III) shown above.

[0056] The organic polymer is preferably selected from poly(arylene ether), polysulfone, polyethersulfone, polyimide, polyamide, polyurea, polyurethane, polyphthalamide, polyamideimide, poly(benzimidazole), and polyaramid.

[0057] Organic polymers are also, in one embodiment herein, of formula (XIII) [ka] [In the formula, Ar 1 Ar 2 Ar 3 and Ar 4 The polymer may be a poly(arylene ether) containing polymer repeating units along a backbone having a structure in which [the aryl radicals are the same or different aryl radicals, m=0 to 1.0, and n=1-m].

[0058] In a further preferred embodiment, the organic polymer is a polymer having aromatic groups in its backbone, preferably a poly(arylene ether), where m is 1 and n is 0, and the polymer is of formula (XIV): [ka] It has repeating units along its framework, which has a specific structure.

[0059] The organic polymer composition may further contain one or more additives. Preferably, the additives are one or more reinforcing fibers, which are continuous or discontinuous, long or short fibers selected from one or more of the following: carbon fibers, glass fibers, woven glass fibers, woven carbon fibers, aramid fibers, boron fibers, polytetrafluoroethylene (PTFE) fibers, ceramic fibers, and polyamide fibers; and / or carbon black, silicate, fiberglass, calcium sulfate, boron, ceramic, polyamide, asbestos, fluorographite, aluminum hydroxide, barium sulfate, calcium carbonate, magnesium carbonate, silica, alumina, aluminum nitride, borax (sodium borate), activated carbon, perlite, zinc terephthalate, graphite, talc, mica, silicon carbide whiskers or plates, nanofillers, molybdenum disulfide, fluoropolymer fillers, carbon nanotubes, and fullerenes. Selected from one or more fillers selected from the tube.

[0060] The additives preferably include reinforcing fibers, i.e., carbon fibers, polytetrafluoroethylene (PTFE) fibers, and / or glass fibers, which are continuous or discontinuous, long or short fibers. Most preferably, the additives are reinforcing fibers and continuous long fibers. In preferred embodiments, the organic polymer composition contains about 0.5% to about 65% by weight of the additive in the composition, more preferably about 5.0% to about 40% by weight of the additive in the composition. The organic polymer composition may further contain one or more stabilizers, flame retardants, pigments, dyes, plasticizers, surfactants, and / or dispersants.

[0061] In another embodiment of the present invention, the crosslinking composition comprises a crosslinking compound having the structure described above, and a crosslinking reaction additive. The crosslinking reaction additive is selected from organic acids and / or acetate compounds and can form a reactive intermediate in the form of an oligomer, the reactive intermediate oligomer can crosslink an organic polymer. The crosslinking reaction additive may be an organic acid such as glacial acetic acid, formic acid and / or benzoic acid.

[0062] The crosslinking reaction additive is given by formula (XII): [ka] [wherein M is a group I or group II metal; R 4 R is an alkyl, aryl, or aralkyl group, where the alkyl group is a hydrocarbon group having 0 to about 10 ester or ether groups, preferably about 0 to about 5 ester or ether groups, along or within the chain of hydrocarbon groups, and has 1 to about 30 carbon atoms, preferably about 1 to about 15 carbon atoms. 4 The acetate compound may have a structure comprising one or more of the following functional groups: sulfate, phosphate, hydroxyl, carbonyl, ester, halide, mercapto, or potassium, and may have 0 to about 10, preferably about 0 to about 5 functional groups. More preferably, the acetate compound may be lithium acetate hydrate, sodium acetate and / or potassium acetate, as well as their salts and derivatives.

[0063] The weight percentage ratio of the crosslinking compound to the crosslinking reaction additive may be about 10:1 to about 10,000:1, more preferably about 20:1 to about 1,000:1.

[0064] In another embodiment, the present invention includes an organic polymer composition for use in forming a crosslinked organic polymer, comprising a crosslinked compound having a structure selected from formulas (I), (II), and (III) described above; a crosslinking reaction additive selected from organic acids and / or acetate compounds; and at least one organic polymer, wherein the crosslinking reaction additive can react with the crosslinked compound to form a reactive intermediate in the form of an oligomer, the reactive intermediate oligomer can crosslink the organic polymer.

[0065] In further embodiments, the present invention includes an organic polymer composition for use in forming a crosslinked organic polymer, comprising an organic polymer and a crosslinked compound having a structure selected from the group of formulas (I), (II), and (III) described above, and a crosslinking reaction additive selected from organic acids and / or acetate compounds, which is a reactive crosslinked oligomer. Preferably, the weight percentage ratio of the organic polymer to the total weight of the crosslinked compound and crosslinking reaction additive is about 1:1 to about 100:1.

[0066] The organic polymer can be selected from any of the organic polymers discussed above. Furthermore, if the organic polymer is a polyarylene ether, it may have repeating units according to the structure of formula (XIII) or it may have the structure of formula (XIV).

[0067] The crosslinked composition may further contain at least one of the additives discussed above, and the composition may contain at least one additive in an amount of 0.5% to about 65% by weight. The crosslinked composition may further contain one or more of stabilizers, flame retardants, pigments, plasticizers, surfactants, and dispersants.

[0068] Crosslinked compositions can be used to form molded articles. These articles are formed using extrusion, injection molding, blow molding, blown film molding, compression molding, or injection / compression molding. Products are selected from acid-resistant coatings, chemically cast films, extruded films, solvent-cast films, blown films, encapsulation products, thermal insulation materials, packaging materials, composite cells, connectors, and sealing assemblies in the form of O-rings, V-rings, U-cups, gaskets, bearings, valve seats, adapters, wiper rings, chevron back-up rings, and tubing.

[0069] Methods for controlling the crosslinking reaction rate of the types of crosslinking compounds described herein, for use in crosslinking organic polymers, are also provided herein. The method comprises the steps of preparing a crosslinking composition comprising a crosslinking compound having a structure selected from the group consisting of formulas (I), (II), and (III) shown above, and a crosslinking reaction additive selected from organic acids and / or acetate compounds, and heating the crosslinking composition so that oligomerization of the crosslinking compound occurs. In some embodiments, the crosslinking composition comprises one or more additional crosslinking compounds.

[0070] In one embodiment, the method further includes the step of heating the crosslinked composition before thermoforming. In an alternative embodiment, the method further includes the step of heating the crosslinked composition during thermoforming.

[0071] The crosslinking compound used in the method for controlling the crosslinking reaction rate may have any of the various structures described above. In one embodiment, the crosslinking reaction additive is an organic acid selected from glacial acetic acid, formic acid and / or benzoic acid, and / or an acetate compound selected from lithium acetate hydrate, sodium acetate and / or potassium acetate and its salts and derivatives.

[0072] In one embodiment, a method for controlling the crosslinking reaction rate further includes the step of combining the crosslinking compound and the crosslinking reaction additive in a solvent and reacting the crosslinking compound and the crosslinking reaction additive to form a reactive oligomerized crosslinking compound. In an alternative embodiment, a method for controlling the crosslinking reaction rate further includes the step of combining the crosslinking compound with the crosslinking reaction additive in solid form.

[0073] A method for controlling the crosslinking reaction rate may include the steps of adding a reactive oligomerized crosslinking compound to an organic polymer to form a crosslinkable composition, and crosslinking the organic polymer composition to form a crosslinked organic polymer.

[0074] In the method for controlling the crosslinking reaction rate, the organic polymer may be any of the organic polymers discussed above. The organic polymer may also be a polyarylene ether containing polymer repeating units with the structure of formula (XIII).

[0075] As acknowledged by the applicant in U.S. Patent No. 9,109,080, incorporated herein by reference in the relevant section, as the viscosity of an aromatic group-containing organic polymer increases, such crosslinking reaction additives can be used for rate control to achieve The degree of inhibition that can be achieved is not always sufficient, and as a result, in some embodiments, additional modifications are desired to improve the final effect by reducing and / or controlling the curing and crosslinking rates. U.S. Patent No. 9,109,080 identifies debrominated organic polymers for crosslinking, but this patent provides limited crosslinking compounds that may be difficult and / or expensive to manufacture.

[0076] The present invention provides debrominated organic polymers for crosslinking, particularly useful for organic polymers having aromatic groups in their skeleton and / or falling within the category of high glass transition temperature polymers, as well as compositions comprising such dehalogenated organic polymers, and methods for preparing and crosslinking them using the crosslinking compounds of formulas (I), (II), and (III) discussed above. The resulting products are formed using a controlled crosslinking reaction rate, and the high processability of the dehalogenated organic polymers allows the use of conventional molding techniques during the crosslinking of such polymers. As previously acknowledged by the applicant, this enables the production of a variety of unique and easily formed crosslinked organic polymer products, providing advantageous properties of such materials, including chemical resistance, high temperature and pressure performance, and strength, for a variety of end applications.

[0077] This specification includes organic polymer compositions for use in the formation of crosslinked aromatic polymers, comprising a dehalogenated organic polymer and at least one crosslinked compound having a structure selected from the group of formulas (I), (II), and (III) described in detail above. The dehalogenated organic polymer is formed by a process comprising the step of reacting an organic polymer having at least one halogen-containing reactive group with an alkali metal compound to form an intermediate by cleaving the bond between the organic polymer having at least one halogen-containing reactive group and the halogen atom in at least one halogen-containing reactive group.

[0078] In one embodiment, the dehalogenated organic polymer is a debrominated organic polymer, and the organic polymer may be any of the polymer types discussed above, or it may be a polyarylene ether having polymer repeating units according to formula (XIII). Furthermore, the organic polymer composition may further contain a crosslinking reaction additive selected from organic acids and / or acetate compounds, the crosslinking reaction additive can react with the crosslinking compound to form a reactive intermediate in the form of an oligomer, the reactive intermediate oligomer can crosslink the dehalogenated organic polymer.

[0079] Dehalogenated organic polymers can be formed by reacting an organic polymer having at least one halogen-containing reactive group with an alkali metal compound to cleave the bond between the organic polymer having at least one halogen-containing reactive group and the halogen atom in at least one halogen-containing reactive group, thereby forming a carbocation-containing intermediate, as described in U.S. Patent No. 9,109,080, which is attributed to the applicant and incorporated herein in the relevant portion. The carbocation-containing intermediate is reacted with acetic acid to form a debrominated organic polymer. In one embodiment, the halogen-containing reactive group is a bromine-containing reactive group.

[0080] In such dehalogenation reactions, alkali metal compounds are preferably structured R 5 -M''[wherein M'' is an alkali metal, R 5 H, or a branched or linear organic group, which is a branched or linear organic group selected from alkyl, alkenyl, aryl and aralkyl groups having 0 to about 10 ester or ether groups along or within the chain or structure of the group, and R 5 It has the characteristic [which may or may not be substituted].

[0081] In one preferred embodiment of this specification, the alkali metal compound is t-butyllithium. This may be done. An organic polymer having at least one halogen-containing terminal group, such as a bromine-containing reactive group, is preferably reacted with an alkali metal compound in a solvent, and the organic polymer having at least one halogen-containing terminal group is preferably dried in the solvent before the reaction. The reaction is carried out at a low temperature until most of the halogen atoms are removed from the organic polymer.

[0082] Organic polymer compositions can be used to form molded articles. These articles may be formed using extrusion, injection molding, blow molding, inflation film molding, compression molding, or injection / compression molding. Products can be selected from acid-resistant coatings; chemical casting films; extruded films; solvent casting films; inflation films; encapsulation products; thermal insulation materials; packaging materials; composite cells; connectors; sealing assemblies including O-rings, V-rings, U-cups, and gaskets; bearings; valve seats; adapters; wiper rings; V-shaped lining rings; and tubing.

[0083] After dehalogenation of an organic polymer, the polymer can be introduced into a crosslinking reaction to provide enhanced performance for such a reaction. Thus, the present invention includes a method for controlling the crosslinking reaction rate of an organic polymer having at least one halogen-containing reactive group, preferably an aromatic group in the polymer's backbone chain, during the crosslinking reaction. The method includes (a) reacting an organic polymer having at least one halogen-containing reactive group with an alkali metal compound to cleave the bond between the organic polymer having at least one halogen-containing reactive group and the halogen atom in at least one halogen-containing reactive group, thereby forming a carbocation intermediate; (b) reacting the carbocation intermediate with acetic acid to form a dehalogenated organic polymer; and (c) crosslinking the dehalogenated organic polymer using a crosslinking compound according to formula (I), (II), or (III) described herein using a crosslinking reaction.

[0084] At least one halogen-containing reactive group is generally a terminal group, and the organic polymer may be any of those described above, such as poly(arylene ether), polysulfone, polyethersulfone, polyimide, polyamide, polyurea, polyurethane, polyphthalamide, polyamideimide, poly(benzimidazole), and polyaramid, preferably having an aromatic group in the polymer's backbone chain.

[0085] At least one halogen-containing reactive group is preferably -R 6 -(X) p [In the formula, R 6 R is a branched or linear organic group selected from 1 to about 30 alkyl, alkenyl, aryl and aralkyl groups having 0 to about 10 ester or ether groups, preferably 0 to about 5 such groups, along or within the chain or structure of the group, and R 6 [where p is a halogen atom and p is an integer, either 1 or 2] is represented by [where p is a halogen atom and p is an integer, either 1 or 2].

[0086] In one embodiment of this specification, the alkali metal compound is R 5 -M'[wherein M' is an alkali metal, R 5 H, or a branched or linear organic group, wherein the branched or linear organic group is selected from alkyl, alkenyl, aryl and aralkyl groups comprising 1 to about 30 carbon atoms, preferably 0 to about 5 such groups, having 0 to about 10 ester or ether groups along or within the chain or structure of the group, and R 5 The group is selected from the group consisting of [which may or may not be substituted].

[0087] An organic polymer having at least one halogen-containing terminal group is reacted with an alkali metal compound in a solvent, preferably according to embodiments of the method described herein. The solvent is preferably capable of dissolving the organic polymer having at least one halogen-containing reactive group and is capable of halogen-containing reaction under the reaction conditions in step (a) described above. It does not contain functional groups that react with halogens in the group. Suitable solvents include heptane, hexane, tetrahydrofuran, and diphenyl ether. Furthermore, the organic polymer having at least one halogen-containing terminal group is preferably dried in the solvent before reacting with an alkali metal compound.

[0088] The first reaction step of the dehalogenation treatment takes place at a temperature preferably lower than about -20°C, preferably lower than about -70°C, for about 2 hours.

[0089] Step (c) of the method for controlling the crosslinking reaction rate of the organic polymer described above is to dehalogenate the organic polymer as follows: [ka] [ka] [Here, Q is a bond, A is an alkyl, aryl, or arene moiety having a molecular weight of less than approximately 10,000 g / mol, and R 1 , R 2 and R 3 The step involves reacting a crosslinked compound having a molecular weight of less than approximately 10,000 g / mol and a structure selected from the group consisting of hydrogen, hydroxyl (-OH), amine (-NH2), halide, ether, ester, amide, aryl, arene, or branched or linear saturated or unsaturated alkyl chains of 1 to approximately 6 carbon atoms, where m is 0 to 2, n is 0 to 2, m+n is greater than 0 or equal to 0 and less than 2 or equal to 2, Z is selected from the group consisting of oxygen, sulfur, nitrogen, and branched or linear saturated or unsaturated alkyl chains of 1 to approximately 6 carbon atoms, where x is approximately 1.0 to approximately 6.0.

[0090] Step (c) further comprises a step of preparing a crosslinking reaction additive selected from organic acids and / or acetate compounds, the crosslinking reaction additive which can react with the crosslinking compound to form a reactive intermediate in the form of an oligomer, the reactive intermediate oligomer which can crosslink a dehalogenated organic polymer.

[0091] Step (c) described above may also include heating the crosslinking compound of the type described above and the crosslinking reaction additive in another composition so that oligomerization of the crosslinking compound occurs to form a reactive intermediate oligomer. The method may also include adding the reactive intermediate oligomer to a dehalogenated organic polymer to form a crosslinkable composition, and then crosslinking the crosslinkable composition to form a crosslinked organic polymer.

[0092] In another embodiment described herein, the present invention relates to a method for preparing an elastomer material, comprising the steps of (a) preparing an aromatic polymer that is a non-elastomer at room temperature; (b) crosslinking the aromatic polymer with a crosslinking compound having a structure selected from the group of formulas (I), (II), and (III) to form a substantially cured crosslinked aromatic polymer; and (c) heating the crosslinked aromatic polymer to the glass transition temperature of the crosslinked aromatic polymer or a higher temperature.

[0093] In one embodiment of a method for preparing an elastomer material, in step (b), the aromatic polymer is cured at least about 80%, preferably at least about 90%, and more preferably completely.

[0094] The aromatic polymer used in the method may be selected from the group consisting of poly(arylene ether), polysulfone, polyethersulfone, polyarylene sulfide, polyimide, polyamide, polyurea, polyurethane, polyphthalamide, polyamideimide, poly(benzimidazole), polyarylate, liquid crystal polymer (LCP), and polyaramid. In one embodiment, the aromatic polymer is a poly(arylene ether) containing polymer repeating units having the structure of formula (XIII) discussed above. Furthermore, in some embodiments, the organic polymer is a poly(arylene ether) containing polymer repeating units having the structure of formula (XIV).

[0095] In one embodiment, step (b) of a method for preparing an elastomer material further comprises crosslinking an organic polymer with a crosslinking reaction additive selected from a crosslinking compound and an organic acid and / or acetate compound, wherein the crosslinking reaction additive can react with the crosslinking compound to form a reactive intermediate in the form of an oligomer, and the reactive intermediate oligomer can crosslink the organic polymer.

[0096] A method for preparing an elastomer material may further include the steps of forming a composition containing a crosslinked organic polymer and heating the composition to form a molded article, wherein step (c) further includes placing the molded article at or above the glass transition temperature of the crosslinked organic polymer at the time of use.

[0097] The present invention further comprises an elastomer material formed by heating a crosslinked aromatic polymer which is substantially cured at or above the glass transition temperature of the crosslinked aromatic polymer, wherein the aromatic polymer is not an elastomer at room temperature prior to crosslinking, and the aromatic polymer is crosslinked by reaction with a crosslinking compound or by heat-induced crosslinking of an aromatic polymer grafted to the aromatic polymer.

[0098] The present invention includes elastomer articles formed by thermoforming a composition containing a crosslinked aromatic polymer that is substantially cured rather than an elastomer at room temperature before crosslinking, and then heating the article at or above the glass transition temperature of the crosslinked aromatic polymer. The aromatic polymer is crosslinked by reaction with a crosslinking compound or by heat-induced crosslinking of aromatic polymers grafted onto the aromatic polymer. The elastomer articles are used for O-rings, V-cups, U-cups, gaskets, sealing laminates, packer elements, and more. The group consists of at least one component of an ear phragm, seal, bearing, valve seat, adapter, wiper ring, V-shaped seal backing ring, and tubing.

[0099] The present invention also includes a method for using an organic polymer that is not an elastomer at room temperature in an elastomer application, comprising the steps of: using a crosslinking compound selected from formula (I), (II), or (III) to crosslink the organic polymer to form a crosslinked organic polymer and substantially cure the aromatic polymer; and, at the time of use, heating the crosslinked polymer to the glass transition temperature of the crosslinked aromatic polymer or a higher temperature, thereby causing it to become an elastomer.

[0100] The method may further include the steps of forming a composition containing a crosslinked organic polymer, molding the composition into a molded article, placing the molded article in use, and heating the molded article in use to heat the crosslinked polymer to the glass transition temperature of the crosslinked polymer or a higher temperature.

[0101] The present invention further includes embodiments comprising a method for preparing an elastomer material. The method is (a) preparing an aromatic polymer that is a non-elastomer at room temperature; and (b) crosslinking the aromatic polymer using a crosslinking compound to form a crosslinked aromatic polymer, wherein the crosslinking compound is as follows: [ka] [ka] [Here, Q is a bond, A is an alkyl, aryl, or arene moiety having a molecular weight of less than approximately 10,000 g / mol, and R 1 , R 2 and R 3 is selected from the group consisting of hydrogen, hydroxyl (-OH), amine (-NH2), halide, ether, ester, amide, aryl, arene, or branched or linear saturated or unsaturated alkyl groups with 1 to about 6 carbon atoms, m is 0 to 2, n is 0 to 2, m+n is greater than 0 or equal to 0 and less than 2 or equal to 2, and Z is oxygen, sulfur, nitrogen, and The method comprises (c) a step of heating the crosslinked aromatic polymer to the glass transition temperature of the crosslinked aromatic polymer or a temperature higher than the glass transition temperature of the crosslinked aromatic polymer.

[0102] In a method for preparing an elastomer material, in step (b), the aromatic polymer is preferably cured to at least about 80%, more preferably to at least about 90%, and most preferably completely cured. The aromatic polymer in the method may be one or more of poly(arylene ether), polysulfone, polyethersulfone, polyarylene sulfide, polyimide, polyamide, polyurea, polyurethane, polyphthalamide, polyamideimide, poly(benzimidazole), polyarylate, liquid crystal polymer (LCP), and polyaramid.

[0103] In one embodiment, the aromatic polymer is a poly(arylene ether) containing polymer repeating units having the structure of formula (XIII) discussed above. In some embodiments, the organic polymer is a polyarylene ether according to formula (XIV).

[0104] In this method, step (b) may further include crosslinking an organic polymer using a crosslinking compound and a crosslinking reaction additive selected from the organic acids and / or acetate compounds discussed above, wherein the crosslinking reaction additive can react with the crosslinking compound to form a reactive intermediate in the form of an oligomer, and the reactive intermediate oligomer can crosslink the organic polymer.

[0105] In another embodiment of the present invention, the present invention relates to a method for improving the extrusion resistance and creep resistance of components used in high-temperature sealing elements or seal connectors, comprising the steps of: preparing a composition comprising an aromatic polymer and a crosslinked compound having a structure according to formula (I), formula (II), and / or formula (III); and subjecting the composition to a thermoforming process to form components and crosslink the aromatic polymer.

[0106] The aromatic polymer may be one or more of the following: polyarylene polymers, polysulfones, polyphenylene sulfides, polyimides, polyamides, polyureas, polyurethanes, polyphthalamides, polyamideimides, aramids, polybenzimidazoles, and their blends, copolymers, and derivatives. Preferably, the aromatic polymer is a polyarylene polymer and / or a polysulfone polymer, and its blends, copolymers, and derivatives.

[0107] If the aromatic polymer is a polyarylene ether polymer, it may have repeating units of the structure according to formula (XIV).

[0108] If the aromatic polymer is a polyarylene type polymer, it is preferably at least one of polyether ether ketone, polyether ketone, polyether ketone ether ketone ketone, polyether ketone ketone, polysulfone, polyphenylene sulfide, polyether sulfone, polyaryl sulfone, and blends, copolymers, and derivatives thereof.

[0109] A composition for forming a sealant resistant to overflow may also include a crosslinking reaction additive that can react with a crosslinking compound to form a reactive intermediate in the form of an oligomer, the reactive intermediate oligomer being able to crosslink an organic polymer. The crosslinking reaction additive may be an organic acid, which may be glacial acetic acid, formic acid, and / or benzoic acid. In another embodiment, the crosslinking reaction additive is an acetate compound having the structure of formula (XII). That's fine.

[0110] The composition for forming a sealant resistant to overflow is an unfilled composition that can be made more ductile in use, or, if desired by the user, can be filled to alter the properties of the composition.

[0111] The present invention also includes sealing components for sealing assemblies formed by a method comprising the step of crosslinking a composition described herein. Sealing connectors having a sealing connector body formed by a method comprising the step of crosslinking a composition described herein are also included herein.

[0112] Furthermore, sealing components and sealing connectors formed by methods for improving the extrusion resistance and creep resistance of components used in the high-temperature sealing elements or sealing connectors described above are also included herein, and the compositions may or may not be filled. The sealing components are sealing backing elements, packer elements, labyrinth seals or double-lip sealing components.

[0113] The above summary, as well as the following detailed description of preferred embodiments of the present invention, will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the present invention, currently preferred embodiments are shown in the drawings. However, it should be understood that the present invention is not limited to the precise configurations and means shown. [Brief explanation of the drawing]

[0114] [Figure 1] Figure 1 shows a graph of dynamic viscosity measurements over time during crosslinking of an organic polymer composition.

[0115] [Figure 2]Figure 2 is a photograph of a conventional PEEK-backed ring tested for 24 hours at 300°F (149°C) with a hydrostatic pressure of 21,000 psi applied to the top surface. A protrusion of 0.19 mm was measured at the outer edge of the ring.

[0116] [Figure 3] Figure 3 is a photograph of the underside of a conventional PEEK-backed ring tested for 24 hours at 450°F (237°C) with a hydrostatic pressure of 11,000 psi applied to the top surface. This high-temperature load caused a 0.30 mm overhang, a 60% increase in overhang, exceeding that of Figure 1, but with only half the applied pressure.

[0117] [Figure 4] Figure 4 shows a conventional SealConnect® connector made from polyetherketone (PEK) before and after applying a hydrostatic pressure of 20,000 psi at 300°F (149°C) for 24 hours.

[0118] [Figure 5] Figure 5 is a differential scanning calorimetry graph showing heat flow as a function of temperature, for heating in the second heating step for each of the inventive blend and comparative samples.

[0119] [Figure 6] Figure 6 shows the rheological time sweep at 380°C from a parallel plate rheometer for the inventive blend and comparative samples. [Modes for carrying out the invention]

[0120] Crosslinking compounds for forming crosslinked organic polymers are described herein. Furthermore, crosslinking compositions comprising crosslinking compounds and one or more reactive crosslinking additives are provided. Organic polymer compositions for use in the formation of crosslinked organic polymers, such combinations Methods for preparing products and polymers, as well as products formed from and by the aforementioned compositions that are useful in end uses under extreme conditions such as underground applications and / or as alternatives to conventional elastomers, are also within the scope of the present invention.

[0121] The present invention provides polymeric materials having thermal stability at high temperatures, and methods and compositions for crosslinking high glass transition polymers to form thermally stable crosslinked polymer systems. In particular, the compositions of this disclosure provide novel additional crosslinkers for high glass transition polymers as a low-cost alternative that is easier to process compared to the applicant's prior crosslinkers exemplified in U.S. Patent No. 9,006,353.

[0122] The crosslinked compounds of the present invention can be synthesized using a Grignard reaction in which an alkyl, vinyl, or arylhalide magnesium, known as a Grignard reagent, is added to a carbonyl group in an aldehyde or ketone to form one or more carbon-carbon bonds. This reaction can be carried out under relatively mild reaction conditions compared to those used to prepare the crosslinking agent of U.S. Patent No. 9,006,353. Furthermore, while U.S. Patent No. 9,006,353 may require the hazardous chemical reactant tert-butyllithium, this is not required for the synthesis of the crosslinked compounds of the present invention. Moreover, the use of mild reaction conditions and less hazardous chemicals allows the crosslinked compounds of the present invention to be prepared at a lower cost.

[0123] In the illustrative example, the crosslinked compound of the present invention can be formed by the following reaction. [ka]

[0124] This reaction can be carried out at room temperature and does not require the use of harsh or extremely hazardous chemicals, enabling the formation of crosslinked compounds as shown.

[0125] The crosslinked high glass transition temperature polymers according to this disclosure are thermally stable at temperatures above 260°C, above 400°C, or up to about 500°C, or above 500°C. The compositions according to this disclosure can be used with unmodified polymers. Polymers with thermal stability up to 500°C present opportunities for fabrications in terms of the usefulness of their scope of application. There are numerous product applications that require polymer components with thermal stability up to 500°C. Some embodiments of this disclosure involve a high crosslink density. By having a high crosslink density, the glass transition temperature of the formed polymer is inherently increased and its susceptibility to swelling when exposed to a solvent is reduced.

[0126] As previously acknowledged by the applicant in U.S. Patent No. 9,006,353, there are advantages to achieving crosslinking by adding crosslinking additives to an unmodified polymer compared to modifying the polymer by grafting crosslinked portions onto the polymer. Previously, polymer modification required dissolving the polymer in a suitable solvent so that the crosslinked portions could be chemically grafted onto the polymer. To overcome this limitation, U.S. Patent No. 9,006,353 Patents 9,109,080 and 9,109,080 disclose crosslinking compounds, crosslinking compositions, methods for forming crosslinked organic polymers, and molded articles formed therefrom. However, the crosslinking compounds in these patents relate to a limited range of compounds that can be expensive or difficult to manufacture. As a result, there is a continuing demand in the art for a variety of crosslinking compounds that are effective as crosslinking agents and can be manufactured more efficiently and easily.

[0127] In this specification, one or more crosslinking compounds are present in crosslinking compositions and organic polymer compositions. Preferably, the crosslinking compound has at least one of the following structures, or the crosslinking compound is a blend of compounds having the following structures, or the crosslinking compound is a blend of one or more compounds having the following structures with one or more additional crosslinking agents, such as those disclosed in U.S. Patent No. 9,006,353, and the present invention provides crosslinking compounds having the following structures: [ka] In formula (III), Q is a bond, and in formulas (I) and (II), A may be Q, an alkyl, aryl, or arene moiety. Partial A, whether alkyl, aryl, or arene, preferably has a molecular weight of less than about 10,000 g / mol. In addition, R 1 , R 2 and R 3 Each of them has a molecular weight of less than approximately 10,000 g / mol. 1 , R 2 and R 3 Each of these is selected from the group consisting of hydrogen, hydroxyl (-OH), amine (-NH2), halide, ether, ester, amide, aryl, arene, or branched or linear saturated or unsaturated alkyl groups having 1 to about 12 carbon atoms, preferably 1 to about 6 carbon atoms. 1 , R 2 and R 3 Each of these may be the same group, R 1 , R 2 and R 3 Two of them may be the same and the third may be different, or they may each be different from one another. In equation (I), m is between 0 and 2, n is between 0 and 2, and m+n is greater than 0 or equal to 0 and less than 2 or equal to 2, and as a result, in some embodiments, R 2 Base R 3 Does not exist at all, R 2 and R 3 Both exist, or two R 2 One or two R 3 One of the groups is present. In formula (I), Z is further selected from the group of oxygen, sulfur, nitrogen, and branched or linear saturated or unsaturated alkyl groups with 1 to about 6 carbon atoms, and x is about 1.0 to about 6.0.

[0128] The crosslinking site is formed by R in any of formulas (I), (II), or (III) to create a more complex crosslinked compound structure. 1This may also include, but is not limited to, the following: [ka]

[0129] The aryl, alkyl, or arene moiety A can be modified and may have different structures, including but not limited to the following: [ka] [ka]

[0130] A is preferably a mirror image of the remainder of the structure shown in formula (I), formula (II), or formula (III). However, in some embodiments, A is 4,4'-biphenyl, i.e. [ka] It may also be a different structure, such as a diradical.

[0131] If desired, the arene, aryl, or alkyl moiety A may also be functionalized with one or more functional groups, such as, for example, sulfate, phosphate, hydroxyl, carbonyl, ester, halide, or mercapto, but not limited to these.

[0132] An organic polymer composition for use in forming a crosslinked polymer comprises the crosslinking compound described above and at least one organic polymer. The at least one organic polymer may be one of several organic polymers with higher glass transition temperatures, including, but not limited to, poly(arylene ether), polysulfone, polyethersulfone, polyimide, polyamide, polyurea, polyurethane, polyphthalamide, polyamideimide, poly(benzimidazole), and polyaramid. Preferably, the polymer is unfunctionalized, chemically inert, and does not have functional groups that would be detrimental to use in underground tool fabrications or end-use applications. However, in some embodiments, the polymer is functionalized as desired to achieve certain properties or as required for a particular application.

[0133] More preferably, the organic polymer is a poly(arylene ether) containing polymer repeating units of the structure according to formula (XIII). [ka] In the formula, Ar 1 Ar 2 Ar 3 and Ar 4 The arene portion of the crosslinked compound may be the same or different aryl radicals from the group listed above, with m=0 to 1.0 and n=1-m.

[0134] More preferably, the organic polymer is a poly(arylene ether) having the structure according to the general structure above, where n is 0 and m is 1, and has repeating units according to formula (XIV). It has a number-average molecular weight (Mn) of approximately 10,000 to 30,000. [ka]

[0135] Such organic polymers are, for example, from Greene, Tweed and Co., Inc., Kulpsville, Pennsylvania to Ultura. TM It can be commercially available as such.

[0136] A crosslinked composition containing the crosslinking compound described above is mixed with a polymer to form a homogeneous mixture. Blending the crosslinking compound with the polymer may be carried out in various ways. One such method is to dissolve both the polymer and the crosslinking compound in a common solvent, and then remove the solvent by evaporation or by adding a non-solvent to induce coprecipitation of the polymer and the crosslinking compound. In some cases, a common solvent may not be present, which may be convenient in cases where an alternative blending treatment such as blending in an extruder, ball mill, or freeze grinder is required. The mixing process is carried out at a mixing temperature preferably not exceeding about 250°C, so as not to cause premature curing during the mixing process. In mechanical mixing, the resulting mixture is homogeneous in order to obtain homogeneous crosslinking.

[0137] The mixture is cured by exposing it to a temperature higher than 250°C, for example, between approximately 250°C and approximately 500°C.

[0138] While we do not wish to be constrained by theory, at temperatures above 250°C, the hydroxyl functional groups of the crosslinked compound can dissociate from the remainder of the additive to produce carbocations, which then undergo Friedel-Crafts alkylation of the aromatic polymer, leading to bond formation. This process is repeated with other hydroxyl moieties in the additive to form crosslinks.

[0139] In the embodiments shown below, when the crosslinked compound is heated to 250°C or higher, the hydroxyl functional group dissociates to form a carbocation as follows. [ka]

[0140] Next, the aromatic polymer can be reacted with a carbocation by Friedel-Crafts alkylation to obtain crosslinks of the polymer.

[0141] In another embodiment of the present invention, the crosslinking composition comprises the crosslinking compound and crosslinking reaction additive described above. The crosslinking reaction additive may be an organic acid such as glacial acetic acid, formic acid and / or benzoic acid.

[0142] The crosslinking reaction additive is given by formula (XII) [ka] [wherein M is a group I or group II metal; R 4 R is an alkyl, aryl, or aralkyl group, and the alkyl group is a hydrocarbon group having 0 to about 10 ester or ether groups, preferably about 0 to about 5 ester or ether groups, along or within the chain of hydrocarbon groups, with 1 to about 30 carbon atoms, preferably about 1 to about 15 carbon atoms. 4 The acetate compound may have a structure comprising one or more of the following functional groups: sulfate, phosphate, hydroxyl, carbonyl, ester, halide, mercapto, or potassium, and may have 0 to about 10, preferably about 0 to about 5 functional groups. More preferably, the acetate compound may be lithium acetate hydrate, sodium acetate and / or potassium acetate, as well as their salts and derivatives.

[0143] The weight percentage ratio of the crosslinking compound to the crosslinking reaction additive may be about 10:1 to about 10,000:1, more preferably about 20:1 to about 1,000:1.

[0144] Crosslinking compounds and crosslinking reaction additives can be reacted to form reactive oligomerized crosslinking intermediates, which can be reacted in situ with the crosslinkable organic polymer during thermoforming and / or before combining with the crosslinkable organic polymer, and then thermoforming, to form the product. The intermediate oligomer reaction product of the crosslinking compound with the crosslinking reaction additive, when combined with the organic polymer, can allow for control of the crosslinking reaction and enable slower rate thermosetting, resulting in a wider window and better control during thermoforming of the resulting crosslinked organic polymer.

[0145] In another embodiment, the present invention comprises an organic polymer composition for use in forming a crosslinked organic polymer, comprising: a crosslinking compound having a structure selected from one or more of the above formulas (I), (II), and (III); a crosslinking reaction additive selected from organic acids and / or acetate compounds; and at least one organic polymer, wherein the crosslinking reaction additive can react with the crosslinking compound to form a reaction intermediate in the form of an oligomer, the reactive intermediate oligomer can crosslink the organic polymer.

[0146] In further embodiments, the present invention includes an organic polymer composition for use in forming a crosslinked organic polymer, comprising an organic polymer, a reactive crosslinked oligomer which is a reaction product of a crosslinked compound having a structure selected from the group of formulas (I), (II), and (III) described above, and a crosslinking reaction additive selected from organic acids and / or acetate compounds.

[0147] Also described herein are crosslinked organic polymer compositions that can provide suppressed and / or controlled crosslinking reaction rates, as well as methods for molding products from crosslinked organic polymers using such compositions. The compositions and methods herein allow for the easier use of traditional (or non-traditional) thermoforming techniques in processes where the curing rate is incompatible. This allows for the formation of parts from crosslinked organic compounds without worrying about the window of crosslinking, resulting in reduced or eliminated premature crosslinking hardening during part formation and obtaining homogeneous parts formed from compositions that are simpler to process.

[0148] Generally, crosslinking in organic polymers that crosslink themselves, or in organic polymer compositions containing unmodified crosslinking compounds, can be completed within about 2 minutes at approximately 380°C, the typical processing temperature for polyether ether ketone (PEEK). The extent of this reaction can be tracked by dynamic viscosity measurements. Two methods are often used to determine when the reaction may be complete. The point where the storage modulus G' equals the loss modulus G'' is called the intersection or gelation point and indicates the start of gel formation where crosslinks interlock. As curing continues, G', an indicator of crosslink density, increases. As curing continues, G' eventually levels off, indicating that most curing is complete. The inflection point G' indicates the start of vitrification and can also be used in cases where a clear intersection cannot be determined (see Figure 1). The time required to reach the intersection of G' and G'' or the start of vitrification can be used as an upper limit on the process time for thermosetting materials.

[0149] As previously described by the applicant in U.S. Patent No. 9,109,080, which is borne by the applicant and incorporated herein by reference in the relevant portion, the use of one or more crosslinking reaction additives in the present invention helps to impart a high glass transition temperature and a high crosslink density to the polymer. Polymers with high thermal stability up to 500°C and a high crosslink density, while desirable, exhibit a very high melt viscosity before further processing and are therefore very difficult to melt process. Since the curing of crosslinked polymers can begin during the thermoforming process, it is desirable to control when crosslinking begins. If the rate of crosslinking is not controlled before the molding of the composition into the final product, the product may begin to cure prematurely or too quickly before or during thermoforming, resulting in incomplete filling into the mold, equipment damage, and deterioration of the product's properties. Thus, crosslinking reaction additives help to improve the control of the rate of crosslink formation in organic polymers. The present invention provides a novel additional crosslinking compound that is easier to produce than previous crosslinking compounds and can be used for crosslinking organic polymers together with crosslinking reaction additives, delaying the onset of crosslinking of organic polymers by several minutes, enabling controlled and rapid processing and shaping of the resulting organic polymer structure.

[0150] The crosslinking reaction additive comprises an organic acid and / or acetate compound that can promote the oligomerization of the crosslinked compound. In one embodiment, oligomerization can be performed by an acid catalyst using one or more organic acids, including glacial acetic acid, acetic acid, formic acid, lactic acid, citric acid, oxalic acid, uric acid, benzoic acid, and similar compounds. An oligomerization reaction using one of the crosslinked compounds listed above is as follows: [ka]

[0151] In other embodiments, inorganic acetate compounds (such as those having the structure of formula (XII) below) may be used instead of or in combination with organic acids. [ka] In the formula, M is a group I metal or a group II metal. R in formula (XII) 4 The group may preferably be an alkyl group, an aryl group, or an aralkyl group. For example, R 4 R may be a hydrocarbon group with 1 to about 30 carbon atoms, preferably 1 to about 15 carbon atoms (including linear and isomers of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl). 4 It may also have 0 to about 10 ester or ether groups along or within the chain of hydrocarbon groups, preferably about 0 to about 5 such ester or ether groups. 4 This may include aryl groups and aralkyl groups (including those based on phenyl groups, naphthyl groups, and similar groups, which may contain a lower alkyl group as needed on an aryl structure with 0 to about 10 carbon atoms, preferably about 0 to about 5 carbon atoms). 4 If desired, the structure may further contain 0 to about 10, preferably 0 to about 5, functional groups such as sulfates, phosphates, hydroxyls, carbonyls, esters, halides, mercaptos, and / or potassium.

[0152] By oligomerizing a crosslinked compound using an acetate compound, an oligomerized crosslinked composition identical to that obtained by adding an organic acid can be obtained. The crosslinking reaction additive may be lithium acetate hydrate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, francium acetate, beryllium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate and / or radium acetate, as well as their salts and derivatives. More preferably, the crosslinking reaction additive is lithium acetate hydrate, sodium acetate and / or potassium acetate, as well as salts and derivatives of such compounds.

[0153] The crosslinking composition is preferably about 10:1 to about 10,000:1 to obtain the best results. Preferably, the weight percentage ratio of the crosslinking compound to the crosslinking reaction additive is about 20:1 to about 1000:1. In the production of the crosslinking composition, in one embodiment, the components are combined before the addition of the organic polymer to produce the organic polymer composition. Alternatively, all of these may be combined at the same time.

[0154] The amount of the crosslinking compound in the crosslinking composition is preferably about 70% to about 98% by weight, more preferably about 80% to about 98% by weight, and most preferably about 85% to about 98% by weight, based on the weight of the crosslinking composition. The amount of the crosslinking reaction additive in the crosslinking composition is preferably about 2% to about 30% by weight, more preferably about 2% to about 20% by weight, and most preferably about 2% to about 15% by weight.

[0155] The organic polymer composition preferably has a weight percentage ratio of the total weight of the organic polymer to the crosslinking compound and crosslinking reaction additive of about 1:1 to about 100:1, more preferably about 3:1 to about 10:1, for the best results.

[0156] The amount of crosslinking compound in the organic polymer composition is preferably about 1% to about 50% by weight, more preferably about 5% to about 30% by weight, and most preferably about 8% to about 24% by weight, based on the total weight of the unfilled organic composition containing the crosslinking compound, crosslinking reaction additives, and organic polymer.

[0157] The amount of crosslinking reaction additive in the organic polymer composition is preferably about 0.01% to about 33% by weight, more preferably about 0.1% to about 10% by weight, and most preferably about 0.2% to about 2% by weight, based on the total weight of the unfilled organic polymer composition containing the crosslinking compound, crosslinking reaction additive, and organic polymer.

[0158] The amount of organic polymer in the organic polymer composition is preferably about 50% to about 99% by weight, more preferably about 70% to about 95% by weight, and most preferably about 75% to about 90% by weight, based on the total weight of the unfilled organic polymer composition containing the crosslinking compound, crosslinking reaction additive, and organic polymer.

[0159] The organic polymer composition may be further filled and / or reinforced with one or more additives to improve the modulus, impact strength, dimensional stability, heat resistance, and electrical properties of composites and other fabricated finished products formed using the polymer composition. These additives include, but are not limited to, reinforcing fibers, which are continuous or discontinuous, long or short fibers, and may be any suitable or useful additives known or to be developed in the art, such as carbon fibers, glass fibers, woven glass fibers, woven carbon fibers, aramid fibers, boron fibers, PTFE fibers, ceramic fibers, polyamide fibers, etc.; and / or one or more fillers, such as carbon black, silicate, fiberglass, calcium sulfate, boron, ceramic, polyamide, asbestos, fluorographite, aluminum hydroxide, barium sulfate, calcium carbonate, magnesium carbonate, silica, alumina, aluminum nitride, borax (sodium borate), activated carbon, perlite, zinc terephthalate, graphite, talc, mica, silicon carbide whiskers or plates, nanofillers, molybdenum disulfide, fluoropolymer fillers, carbon nanotubes, and fullerene tubes. Preferably, the additive includes reinforcing fibers such as carbon fibers, PTFE fibers, and / or glass fibers, which are continuous or discontinuous, long or short fibers.

[0160] When manufacturing an organic polymer composition, it is preferable that the additive is added to the composition at the same time as, or almost simultaneously with, the time at which the oligomerized crosslinked composition (or a combination thereof) is combined with the organic polymer to manufacture the organic polymer composition. However, the method of preparing the reinforcing fibers or other fillers may vary depending on the various techniques for incorporating such materials. It should not be considered that this limits the scope of the present invention. The amount of additive is preferably about 0.5% to about 65% by weight, and more preferably about 5.0% to about 40% by weight, based on the weight of the organic polymer composition.

[0161] Furthermore, the organic polymer composition may further contain other compounding agents to assist the manufacturing process, including stabilizers, flame retardants, pigments, plasticizers, surfactants and / or dispersants, such as those known in the art or to be developed. When manufacturing the organic polymer composition, it is preferable that one or more fillers are added to the organic polymer composition at the same time as, or almost simultaneously with, the time at which the oligomerized crosslinked composition (or a combination thereof) is combined with the organic polymer to manufacture the organic polymer composition; however, as described above, the manner in which such materials are prepared may follow a variety of techniques and should not be considered to limit the scope of the present invention. When used, the amount of compounding agents that can be combined with the organic polymer composition is preferably about 5% to about 60% by weight, more preferably about 10% to about 40% by weight, and most preferably about 30% to about 40% by weight, based on the weight of the organic polymer composition.

[0162] In embodiments of the method of the present invention, after being prepared, for example by the preparation of a crosslinked composition as described herein, the crosslinked composition is heated to induce oligomerization of the crosslinked compound. In one embodiment of the method, oligomerization is catalyzed by an acid catalyst. The acid catalyst is used when an organic acid is used as the crosslinking additive. R of the crosslinked compound of formula (I), formula (II), or formula (III) 1 The functional groups can dissociate from the remainder of the compound to yield carbocations, which can then undergo Friedel-Crafts alkylation of the organic polymer to result in bond formation. In another embodiment of the method of the present invention, oligomerization of the crosslinked compound can be achieved by doping. After doping by physically mixing the reactants in solid form in the composition at a low temperature of about -100°C to about -300°C, the entire composition is reacted to cure and / or thermoform the resulting composition to form a product.

[0163] The method may further include the step of adding the reacted oligomerized crosslinked composition to an organic polymer to form a crosslinkable composition. Unmodified crosslinked compounds can be added directly to an organic polymer, blended with a crosslinking reaction additive, and simultaneously oligomerized and bonded to the organic polymer. Once the reactive oligomerized crosslinked compound reacts with the organic polymer, the rate of crosslinking of the organic polymer occurs later in the curing process. As a result, a product is formed that is fully filled into the mold and undergoes superior final thermoforming / extrusion from the composite polymer during various thermoforming techniques.

[0164] The powder of the organic polymer composition of the present invention can be pelletized and subjected to a thermoforming process. Thermoforming of the organic polymer composition can be carried out by various means already known in the art or to be developed, including extrusion, injection molding, compression molding and / or injection / compression molding. Pelletized organic polymer composition of the present invention can be injection molded in an Arbug® 38-ton injection molding machine equipped with a cold runner system including a hot sprue.

[0165] Thermoforming for forming the manufactured product can be carried out by any method known in the art or to be developed (including, but not limited to, thermosetting, curing by application of high energy, press curing, vapor curing, pressure curing, electron beam curing, or curing by any combination of means). If desired, post-curing treatments known in the art or to be developed can also be applied. The organic polymer compositions of the present invention are cured by exposure of the composition to a temperature of about 250°C to about 500°C, more preferably about 350°C to about 450°C or higher.

[0166] The compositions and / or methods described above may be used in downhole tools and applications used in the petrochemical industry and may also be used to prepare their manufactured products. In particular, the manufactured products are selected from the group consisting of acid-resistant coatings, chemically cast films, extruded films, solvent-cast films, blown films, encapsulated products, insulators, packaging materials, composite cells, connectors and O-rings, V-rings, U-cups, gasket-shaped sealing assemblies, bearings, valve sheets, adapters, wiper rings, chevron back-up rings and pipe materials.

[0167] In U.S. Patent No. 9,109,080, which is assigned to the applicant and incorporated herein by reference in relevant part, the applicant has discovered that it is possible to chemically remove halogen from halogen-containing end groups to control halogen-containing by-products and to form a purified organic polymer in the sense that such a polymer is dehalogenated prior to crosslinking. Such dehalogenated purified organic polymers can then be readily crosslinked and shaped, such that the crosslinking reaction during shaping is more slowly and more compatibly controlled and traditional thermoforming techniques can be readily used. However, U.S. Patent No. 9,109,080 is limited to the specific crosslinking compounds described therein, and it is desirable that manufacturing still be easier using a variety of different crosslinking compounds having good performance. Accordingly, the present invention provides crosslinking compounds as described herein that are even more useful in the crosslinking of dehalogenated organic polymers.

[0168] In one embodiment, the present invention provides crosslinked articles formed from crosslinked dehalogenated organic polymers using an organic polymer composition having a dehalogenated organic polymer and a crosslinking compound, a crosslinking compound according to one of formulas (I), (II) and / or (III) described herein and optionally one or more reactive crosslinking additives, and for use in the formation of crosslinked organic polymers. Further, methods of preparing such compositions and polymers, and manufactured products formed by such methods from the foregoing compositions, are within the present invention and are useful in end uses under extreme conditions such as in downhole applications.

[0169] The crosslinked compositions containing a crosslinking compound according to formula (I), (II) or (III) described herein can be reacted to form a reactive oligomerized crosslinking intermediate, in situ during thermoforming with a crosslinkable dehalogenated organic polymer, and / or by reacting another crosslinked composition having a crosslinking compound and a crosslinking reaction additive to form an oligomerized crosslinking intermediate, and then combining the oligomerized crosslinking intermediate with a crosslinkable dehalogenated organic polymer and heating and shaping the combined materials to form an article either way. The intermediate oligomer reaction product of the crosslinking compound with a crosslinking reaction additive as required acts as an inhibitor and generally enables control of the crosslinking reaction when combined with an organic polymer, especially one having an aromatic group in the backbone. However, when a dehalogenated organic polymer is used as the base polymer, it can enable a further lower rate of thermosetting, enabling a wider window and better control during thermoforming, and suppression of the reaction rate.

[0170] The formation of crosslinks in an organic polymer that crosslinks itself or in an organic polymer composition containing an unmodified crosslinking compound can be completed within about 2 minutes at about 380 °C, which is a typical processing temperature of polyetheretherketone (PEEK).

[0171] The use of one or more crosslinking reaction additives can assist in more stably imparting curing with a high glass transition temperature and a high crosslink density to the polymer when combined with a crosslinking compound according to one or more of the formulas (I), (II) or (III) described above. Polymers having a high thermal stability up to 500 °C and a high crosslink density are desirable, but as mentioned above, they exhibit a very high melt viscosity before further processing and thus are very difficult to melt process. If the rate of crosslinking is not controlled before the shaping of the composition into the final article, the fabricated product may start to cure prematurely before or during thermoforming or have a high If the process proceeds too quickly, it can lead to incomplete filling of the mold, equipment damage, and deterioration of the properties of the product. Therefore, the present invention also aims to improve the process by controlling or inhibiting the rate of crosslinking in organic polymers using the crosslinking reaction additives described herein, in combination with the crosslinking compounds and / or dehalogenated organic polymers, such as the debrominated organic polymers, that can be crosslinked, as described herein. This provides a reaction in which the inhibitor (rather than interference by X or HX formation, such as B or HBr) can work more effectively, delaying the onset of crosslinking of the organic polymer by several minutes beyond what can be achieved without the initial dehalogenation treatment of the polymer, and enabling rapid processing and molding of the resulting organic polymer structure in a controlled manner.

[0172] In the organic polymer compositions of this specification for use in the formation of crosslinked organic polymers, the composition comprises at least one dehalogenated organic polymer. Polymers that can benefit in a preferred manner by dehalogenation treatment before crosslinking may be one of several organic polymers with higher glass transition temperatures and / or comprise at least one organic polymer having aromatic groups in the polymer backbone, including, but not limited to, poly(arylene ether), polysulfone, polyethersulfone, polyimide, polyamide, polyurea, polyurethane, polyphthalamide, polyamideimide, poly(benzimidazole) and polyaramid. Preferably, the polymer is unfunctionalized and therefore chemically inert and does not have functional groups that would be detrimental to use in underground tool manufacturing or end-use applications. If it is possible to benefit from dehalogenation treatment before crosslinking, such polymers also have at least one halogen-containing reactive group. Generally, such groups are terminal groups that may remain from polymerization processes or other end-blocking reactions, as discussed above.

[0173] More preferably, in one embodiment of this specification, the organic polymer is a poly(arylene ether) such as those described above, and includes polymer repeating units in the backbone of a polymer chain having the structure of formula (XIII). More preferably, the organic polymer is a poly(arylene ether) having repeating units of formula (XIV) and a number-average molecular weight (Mn) of about 10,000 to about 30,000.

[0174] As described above, other suitable organic polymers used in the present invention, such as polyarylenes and polyarylene ethers, may be produced, for example, using diiodobiphenyl monomers and / or dibromobiphenyl monomers. In such cases, the methods used herein must be used to remove bromine-containing reactive groups or iodine-containing reactive groups in order to deiodize or debrominate the polymer. For other suitable polymers, such as polysulfones, many are formed using chlorinated monomers in synthesis, but chlorine-containing reactive groups may remain, and the methods herein must be used to remove the chlorine from the chlorine-containing reactive groups. Thus, for organic polymers having halogen-containing reactive groups present, from those formed by polymerization processes that leave reactive halogen-containing groups such as halogen-containing terminal groups, it will be understood by those skilled in the art that such organic polymers can be dehalogenated to provide a purified organic polymer in use in crosslinking reactions where rate control is a problem when using such polymers in traditional thermoforming processes.

[0175] To dehalogenate organic polymers, the organic polymers, either alone or in combination, may be subjected to the method described in U.S. Patent No. 9,109,080. The method provides dehalogenated organic polymers that work to control the crosslinking reaction rate of organic polymers having at least one halogen-containing reactive group during the crosslinking reaction in a crosslinked composition. The method uses organic polymers having halogen-containing reactive groups with one or two halogen-containing terminal groups, such as those described above, preferably bromine, iodine, and chlorine.

[0176] A polymer having a halogen-containing reactive group reacts with an alkali metal compound to cleave the bond linking the halogen atom to the polymer, i.e., the bond between the organic polymer having at least one halogen-containing reactive group and the halogen atom of at least one halogen-containing reactive group. This reaction forms an intermediate having a carbocation.

[0177] At least one halogen-containing reactive group is typically a halogen atom (X), but more often the halogen atom is attached to the chain, most typically at a terminal position near the final organic group, away from the main skeleton. Such a reactive group is -R 6 -(X) p [In the formula, R 6 R is a branched or linear organic group selected from alkyl, alkenyl, aryl and aralkyl groups, having 0 to about 10 ester or ether groups, preferably 0 to about 5 ether or ester groups, along or within the chain or structure of the carbon or group, and having 1 to about 30 carbon atoms, preferably 1 to about 20 carbon atoms. 6 This may be expressed as [may be substituted or not]. Suitable alkyls include methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, etc. Suitable alkenyls include methenyl, ethenyl, propenyl, iso-propenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, etc. The aryl group may be monocyclic or polycyclic, such as benzyl, phenyl, xylyl, biphenyl, dibenzyl, and such groups may have an aryl or aralkyl group or side chain and may also be modified to form an aralkyl structure. X represents a halogen, bromine, iodine, chlorine, fluorine, etc., and p is an integer, either 1 or 2.

[0178] The reaction of organic polymers having halogen-containing reactive groups preferably occurs with alkali metal compounds. 5 -M'[wherein M' is an alkali metal, R 5R can be represented by H, or a branched or linear organic group, which may be a branched or linear organic group selected from alkyl, alkenyl, aryl and aralkyl groups having 0 to about 10 ester or ether groups along the chain or structure of the group, preferably 0 to about 5 such groups, and 1 to about 30 carbon atoms, preferably about 1 to about 15 carbon atoms. 5 The substituents may be substituted or unsubstituted. The substituents may include functional groups that provide other properties to the resulting polymer, provided that they do not act on the dehalogenated organic polymer ultimately formed from the process and / or affect the reaction or rate of organic polymers having halogen-containing reactive halogen groups, or adversely affect the reaction of such polymers with alkali metals. Such functional groups may include, for example, hydroxyl, carbonyl, ester, halide, mercapto, and / or potassium.

[0179] Suitable alkali metal compounds include methyllithium, methenyllithium, ethyllithium, ethenyllithium, isopropyllithium, propyllithium, propenyllithium, butyllithium, isobutyllithium, t-butyllithium, s-butyllithium, n-butyllithium, butenyllithium and similar compounds; methylsodium, methenylsodium, ethylsodium, ethenylsodium, isopropylsodium, propylsodium, propenylsodium, n-butylsodium, s-butylsodium, t-butylsodium, butenylsodium and similar compounds; methylpotassium, methenylpotassium, ethylpotassium, ethenylpotassium, propenylpotassium, butylpotassium, isobutylpotassium, n-butylpotassium, s-butylpotassium, t-butylpotassium, butenylpotassium and similar compounds; and, for example, benzyllithium, phenyllithium, benzylsodium, phenylsodium, benzylpotassium, phenylpotassium, and other related compounds. Preferably, alkali metal compounds include butyllithium, t-butyllithium, butylsodium, t-butylsodium, butylcalcium It is potassium t-butyl or potassium t-butyl.

[0180] An organic polymer having at least one halogen-containing terminal group is preferably reacted with an alkali metal compound in a solvent environment. The solvent is preferably capable of dissolving the organic polymer having at least one halogen-containing reactive group, but does not contain a functional group that reacts with the halogen in the halogen-containing reactive group under the reaction conditions used. Suitable solvents include, but are not limited to, heptane, hexane, tetrahydrofuran, and diphenyl ether, as well as similar solvents and derivatives or functionalized variants of such solvents, with tetrahydrofuran (THF) being the most preferred solvent.

[0181] To minimize potential side reactions between the solvent and the alkali metal compound used, the reaction takes place at a low temperature, preferably below about -20°C, preferably below about -50°C, and more preferably below about -70°C. For example, since the half-life of t-butyllithium in THF at -20°C is about 42 minutes, further time is given by reacting it at a temperature below that, e.g., -70°C to -78°C, and the estimated half-life of the compound in THF is about 1,300 minutes. In this way, the reaction proceeds as desired, and interference of reactivity due to thermal issues is minimized. Preferably, the reaction proceeds until most of the halogen atoms are removed from the organic polymer, preferably substantially all of the halogen atoms, most preferably until virtually all or all of the halogen atoms are removed. The reaction time is expected to last about 0.5 to about 4 hours, preferably about 1 to about 2 hours, depending on the solvent, alkali metal compound and reaction temperature used.

[0182] Before introducing an organic polymer into such a solvent reaction, it is preferable to first dry the organic polymer having at least one halogen-containing reactive group to be reacted with the alkali metal compound in the solvent as a preparatory step before reacting the alkali metal compound with the polymer in the solvent. Such a drying step may be carried out in any suitable manner for the purpose of minimizing or removing adsorbed water from the polymer, as water can interfere with the reaction. One acceptable non-limiting method for drying the polymer is to oven dry them in a vacuum oven at a temperature suitable for the chosen polymer. For polyarylene polymers, a temperature of about 100°C to about 200°C, more preferably about 110°C to about 120°C, is suitable. Oven drying should be carried out with the understanding that the drying time can also vary depending on the polymer and the level of adsorbed water in the pre-treated polymer, until the polymer is at least substantially dry for about 10 hours, preferably at least 15 hours, most preferably about 16 hours. Drying can be verified by various types of moisture analysis, such as Karl Fischer coulometric titration of polymers dissolved in THF, dew point measurement in an air dryer, or weight loss by thermogravimetric analysis (TGA) at temperatures below approximately 250°C.

[0183] When a dry organic polymer containing halogen-containing reactive groups dissolves in a solvent and reacts with an alkali metal compound, a carbocation-containing intermediate is formed. This intermediate and the subsequent reaction are then quenched by reacting the carbocation-containing intermediate with acetic acid or a similar acetate group containing an acid to form a dehalogenated organic polymer.

[0184] One reaction scheme for this reaction, using a polyarylene polymer in which the halogen-containing reactive group is diphenylbromine, is shown by the reaction mechanism below. [ka] In the formula, R represents a polymer chain of formula (XX) containing the first phenyl group in the terminal diphenyl bromine group.

Chem.

[0185] The above mechanism shows a method of dehalogenation, but other reactions and methods for removing halogen from such organic polymers may also be used. For example, J. Moon et al., "Hydrogenolysis of Aryl Halides by Hydrogen Gas and Hydrogen Transfer over Palladium-Supported Catalysts,” vol. 3, issue 6, Comptes Rendus L'Académie des Sciences - Chemistry, pp. 465 - 470 (Nov. 2000). Dehalogenation may also be carried out by treatment with a Grignard reagent. Grignard Degradation, Comprehensive Organic Name Reactions and Reagents, pp. 1271 - 1272 (Sept. 2010).

[0186] After the dehalogenation of the organic polymer is carried out by any of the various methods known in the art, the dehalogenated organic polymer can be introduced into a crosslinking reaction with the crosslinking compound of the present invention, providing enhanced performance for such a reaction. Any suitable grafting, reaction or similar crosslinking reaction in which crosslinking occurs, using a crosslinking compound according to one or more of formulas (I), (II) and (III) discussed above, may be used.

[0187] Thus, an organic polymer composition can be formed comprising a dehalogenated organic polymer and a crosslinked compound according to formula (I), (II), or (III). A dehalogenated organic polymer having aromatic groups in its backbone can be crosslinked using a crosslinked compound according to any of the formulas (I), (II), and (III) described above. One or more crosslinked compounds of the present invention are present in a crosslinked composition, and in such a composition, a dehalogenated organic polymer It can be combined with Ma.

[0188] Part A of the crosslinked compound may have any of the structures or features described in detail above.

[0189] The crosslinked composition and the organic polymer composition also include one or more crosslinking reaction additives as rate control compounds as discussed above. The crosslinking reaction additives include organic acids and / or acetate compounds that can promote oligomerization of the crosslinked compound. In other embodiments, inorganic acetate compounds, such as those having the structure of formula (XII), may also be used instead of or in combination with the organic acids discussed above. The crosslinked composition has a weight percentage ratio of the crosslinked compound to the crosslinking reaction additives discussed above and can be combined before or at the same time as the addition of the dehalogenated organic polymer. Furthermore, the weight percentage of the crosslinked compound in the composition is the same as that discussed above.

[0190] When producing an organic polymer composition, it is preferable to combine the crosslinking compound and the crosslinking reaction additive component before adding the dehalogenated organic polymer. Alternatively, they may all be combined at the same time.

[0191] The organic polymer composition may further fill and / or reinforce with one or more additives to improve the modulus, impact strength, dimensional stability, heat resistance, and electrical properties of composites and other fabricated finished products formed using the polymer composition. These additives are any suitable or useful additives known or to be developed in the art as described above.

[0192] When producing an organic polymer composition, it is preferable to add the additive, an oligomerized crosslinked composition (or a combined component thereof), to the composition at the same time as, or almost simultaneously with, the combination with the dehalogenated organic polymer to produce the organic polymer composition. However, the method of preparing reinforcing fibers or other fillers may be according to various techniques for incorporating such materials and should not be considered to limit the scope of the present invention. The amount of the additive is preferably about 0.5% to about 65% by weight, more preferably about 5.0% to about 40% by weight, based on the weight of the organic polymer composition.

[0193] Furthermore, the organic polymer composition may further contain other compounding materials, including stabilizers and flame retardants, as discussed above.

[0194] In embodiments of the crosslinking method according to the present invention, for example, after preparing the crosslinked composition described herein by manufacturing, the crosslinked composition is heated to induce oligomerization of the crosslinked compound.

[0195] In one embodiment of the crosslinking method, oligomerization occurs by the catalytic action of an acid. When an organic acid is used as a crosslinking additive, an acid catalyst is used. R of the crosslinking compound of formula (I), (II), or (III) 1 The functional group can dissociate from the remainder of the compound to yield a carbocation, which can then undergo Friedel-Crafts alkylation of the organic polymer, resulting in bond formation. In another embodiment of the method of the present invention, oligomerization of the crosslinked compound can be induced by doping. Doping is carried out by physically mixing the solid reactants in the composition at a low temperature of about -100°C to about -300°C before reacting the entire composition for curing and / or thermoforming the resulting composition to form a product.

[0196] The crosslinking method may further include the step of adding the reacted oligomerized crosslinked composition to a debrominated organic polymer to form a crosslinkable composition. The unmodified crosslinked compound is dehalogenated. The reactive oligomerized crosslinking compound may be added directly to the organic polymer and blended with a crosslinking reaction additive to simultaneously oligomerize and bond with the dehalogenated organic polymer. When the reactive oligomerized crosslinking compound reacts with the dehalogenated organic polymer, the crosslinking rate of the dehalogenated organic polymer occurs more slowly in the curing process compared to the crosslinking rate that occurs in the organic polymer composition using the same crosslinking system or other prior art crosslinking systems with the inhibitory additive described above, without dehalogenation treatment. As a result, it is possible to more easily form fully filled molds and superior thermoformed works using traditional molding techniques and controlled, longer crosslinking times.

[0197] The powder of the organic polymer composition of the present invention can be made into pellets, and the pellets can be subjected to a thermoforming process. Thermoforming of the organic polymer composition can be carried out by a variety of means already known in the art or to be developed, including extrusion, injection molding, compression molding and / or injection / compression molding. Pellets of the organic polymer composition of the present invention can be injection molded, for example, in an Arbug® 38-ton injection molding machine equipped with a cold runner system including a hot sprue.

[0198] Thermoforming for forming the manufactured product can be carried out by any method known in the art or to be developed as discussed above, and post-curing treatment can also be applied if desired. The organic polymer composition of the present invention is cured by exposure of the composition to a temperature of about 250°C to about 500°C, more preferably above about 350°C to about 450°C.

[0199] The compositions and / or methods described above may be used in underground tools and applications used in the petrochemical industry, and may be used to prepare such products. In particular, the products may be one or more of the following, as discussed above: acid-resistant coatings, chemically cast films, extruded films, solvent-cast films, blown films, encapsulated products, insulating materials, packaging materials, composite cells, connectors and O-rings, V-rings, U-cups, sealing assemblies in the shape of gaskets, bearings, valve seats, adapters, wiper rings, V-shaped backing rings, and tubing.

[0200] Similar to the example of the crosslinked compounds previously invented by the applicant as described in U.S. Patent No. 9,109,075, which is incorporated herein by reference in the relevant portion, the applicant has also determined that, although the crosslinked aromatic polymers formed using the novel crosslinked compounds of the present invention are non-elastomers at room temperature, in particular, the class of crosslinked polyarylene polymers or polyphenylene sulfides becomes essentially elastomer while maintaining excellent mechanical properties when applied to end-use applications above the glass transition temperature of the crosslinked aromatic polymer. Such materials can be used in harsh and high-temperature applications, including those under which FFKM materials may experience degradation. The materials used herein can be crosslinked without complex synthesis, and the crosslinking density can be controlled for different end-use applications. The materials have high temperature stability while maintaining good mechanical properties during use. The thermal stability derives from the skeleton, thereby providing an advantage against thermal degradation over traditional FFKM in high-temperature end-use applications.

[0201] As used herein, “high temperature” application means the application of the organic polymer to the end use within the context of the organic polymer used. g In preferred embodiments using polyarylene polymers and similar high-temperature polymers, which include end applications requiring temperatures approximately 30°C higher, applications at temperatures where traditional FFKMs may experience thermal degradation, such as approximately 330°C, preferably approximately 340°C or higher. gThe material is suitable for temperatures of approximately 150°C or higher. g Includes a material having "low T g The material is suitable for temperatures below approximately 150°C. g Includes materials having . Those skilled in the art will know, based on this disclosure, that "high T g "Materials and "Low T g The temperature division between materials may be stepwise and varied. g It is understood that standard materials can benefit from the inventions described herein.

[0202] Methods for preparing elastomer materials are included herein. In one embodiment, in a first step, an aromatic polymer that is non-elastomer at room temperature is prepared. "Non-elastomer" means a material whose behavior at room temperature or under standard conditions is not that of an elastomer.

[0203] As used herein, the term "elastomer" or "elastomer-like" refers to a polymer that is amorphous above its glass transition temperature, possesses flexibility and deformability, and can be deformed and largely restored to its original state. In this specification, elastomers or elastomer materials are formed as crosslinked chains, and when the applied stress is removed, the elastomer can largely restore its original stereochemistry through crosslinking, rather than permanently deforming.

[0204] Many elastomer materials are evaluated not only by measuring mechanical properties such as tensile strength, flexural strength, elongation, and modulus, but also by assessing the material's ability to recover after deformation. One property evaluated in this context is compression set resistance. As used herein, “compression set” refers to the tendency of an elastomer material to remain bent and not return to its original shape after the deformable compressive load is removed. The compression set value is expressed as a percentage of the original deflection from which the material does not recover. For example, a compression set value of 0% indicates that the material will return completely to its original shape after the deformable compressive load is removed. Conversely, a compression set value of 100% indicates that the material will not recover at all from the applied deformable compressive load. A compression set value of 30% means that 70% of the original deflection has recovered. Higher compression set values ​​generally indicate a possibility of seal leakage, and therefore, a compression set value of 30% or less is preferred in the art of sealing.

[0205] The aromatic polymers herein, which are non-elastomers at room temperature, preferably include polyarylene polymers. A single organic polymer may be crosslinked, or multiple types of such organic polymers may be crosslinked simultaneously, preferably by first combining polymers and then reacting the combined polymers with a crosslinking compound, or by heat-inducing the crosslinking of organic polymers having grafts on the polymer backbone as further described below.

[0206] At least one organic polymer may be one of several organic polymers with higher glass transition temperatures, used alone or in combination, such as, but not limited to, poly(arylene ether), polysulfone, polyethersulfone, polyarylene sulfide, polyimide, polyamide, polyurea, polyurethane, polyphthalamide, polyamideimide, poly(benzimidazole), polyarylate, liquid crystal polymer (LCP), and polyaramid. Preferably, when subjected to reaction with a crosslinking compound, the polymer is unfunctionalized, i.e., chemically inert, and does not have functional groups that would be detrimental to use in underground tool fabrications or other demanding end applications.

[0207] Preferably, the organic polymer is a poly(arylene ether) of formula (XIII) as discussed above. More preferably, and as discussed above, the organic polymer has the structure of formula (XIV).

[0208] Furthermore, polymers formed from thermally induced crosslinking of a polyarylene backbone having at least one graft are within the scope of the present invention. Such materials are described in U.S. Patent No. 6,060,170, which is incorporated herein by reference with respect to the description of the formation of such polymers and the resulting final products. Organic polymers can also be crosslinked directly by the use of crosslinking compounds, as in U.S. Patent No. 9,006,353, or by reaction with crosslinking reaction additives, as further described herein.

[0209] Suitable crosslinked polyarylene organic polymers used in this invention include, for example, high-temperature polymers from Greene, Tweed and Co., Inc., Kulpsville, Pennsylvania, such as Ultra TM It can be commercially available as such.

[0210] The crosslinking compounds may be used as a single compound or as a combination of two or more such crosslinking compounds. They can be used in combination with the organic polymers described above to form the crosslinking compositions herein. The crosslinking compounds have a structure according to one or more of formulas (I), (II), and (III) and are of the type discussed above. As discussed above, the A portion may be modified, functionalized, and A is preferably a bond.

[0211] The preferred organic polymer is Ultura, described above. TMIt includes commercially available materials such as polyether ether ketone, high-temperature polyether ether ketone, crosslinkable grafted polyarylene ether, 1,4-polyarylene ether, and similar polymers. Amorphous polyarylenes such as meta- and ortho-oriented amorphous polyether ether ketone can, if desired, be used to impart elastomeric properties at much lower temperatures, for example, from about 150 °C to about 160 °C. 1,4-Polyarylene ether can be used to obtain a low glass transition temperature in the range of about 100 °C. Polyphenylene sulfide can also be used for similar glass transition temperatures.

[0212] Examples of various 1,4-polyether ether ketones in different orientations are shown below.

Chemical formula

[0213] The structure (XV) above represents a commercially available polyether ether ketone formed using para-hydroquinone monomer. The central (XVI) and lower (XVII) structures above represent ortho-PEEK and meta-PEEK, respectively. The preferred high-temperature commercially available polyarylene ether organic polymers used herein are also shown. Similarly, the names of the authors can be described.

Chemical formula

[0214] Low T g materials, that is, such materials can be used as elastomeric materials, and the use of materials having a T lower than about 150 °C that can benefit from the present invention in high-temperature applications g is preferably for end-use applications having a temperature of about 30 °C or higher than the T of the low T g materials. Similarly, high T g materials, that is, such materials can be used as elastomeric materials, and having a T of about 150 °C or higher that can benefit from the present invention in high-temperature applications g g gThe use of the material preferably has a final use having a temperature of about 30 °C or higher than the T of the high-T material. g The T of the material g is a final use having a temperature of about 30 °C or higher.

[0215] For low-T uses, polyarylene ethers such as 1,4-polyarylene ether having a T of about 90 °C are shown in the following (XVIII). Polyphenylene sulfide has a structure (XIX) and glass transition temperature similar to those of polyarylene ethers, and thus both impart similar elastomeric properties. However, since the thioether bond is not as resistant to oxidation as the ether bond in polyarylene ethers, polyphenylene ether is a preferred base polymer for oxidation-resistant elastomeric compositions for high-oxidation environments.

Chemical formula

Chemical formula

[0216] The crosslinked composition and the organic polymer composition also contain the crosslinking reaction additive discussed above. The crosslinking reaction additive includes an organic acid and / or an acetate compound, preferably an acetate compound having the structure of formula (XII) discussed above.

[0217] The oligomerization reaction using one of the crosslinking compounds can occur as discussed above. The crosslinked composition can have the weight percentage ratios discussed above, and the organic polymer composition can have the same weight percentage ratios as discussed above. The crosslinking compound and the crosslinking reaction additive are preferably combined before the addition of the organic polymer to produce the organic polymer composition as discussed above, or they may be combined simultaneously. The organic polymer composition may be filled or reinforced with one or more of the additives discussed above. The organic polymer composition may further contain other ingredients such as the stabilizers and flame retardants discussed above, among others.

[0218] ​​​​ Adding the reacted oligomerized crosslinked composition to an organic polymer to form a crosslinkable composition is also within the scope of the present invention as needed. Unmodified crosslinked compounds may be added directly to the organic polymer and blended with crosslinking reaction additives to simultaneously oligomerize and bond to the organic polymer. Once the reactive oligomerized crosslinked compound reacts with the organic polymer, the use of crosslinking reaction additives, if used, helps control the rate of crosslinking of the organic polymer, especially for certain aromatic polymers, particularly polyarylene ethers. As a result, products are formed that are fully filled into molds and undergo superior final thermoforming / extrusion from the composite polymer during various thermoforming techniques.

[0219] The compounds crosslink in this manner, as described above, to form crosslinked aromatic polymers that may or may not be filled.

[0220] The crosslinked aromatic polymer is preferably heated to the glass transition temperature of the crosslinked aromatic polymer or a temperature above it. This temperature may vary depending on the properties of the crosslinked organic polymer. For preferred polyarylene polymers, the glass transition temperature is about 80°C to about 350°C, more preferably about 100°C to about 280°C. Heating may be carried out carefully or may occur by the application of heat in the end use application, which may be a high-temperature application, however, it is preferable that the crosslinking is substantially made, i.e., the material is substantially cured, or more preferably completed before use in a high-temperature end use. As used herein, “substantially cured” means that the material has been cured to such an extent that using it in its end use does not affect its potential elastomeric properties, preferably at least about 80%, more preferably at least about 90%, and most preferably up to 100% of the most complete curing possible.

[0221] It is even more preferable to heat the composition to form a molded article after forming the composition having a crosslinked organic polymer therein. The thermoforming to form the article may be carried out by any method known in the art or to be developed, as discussed above. A post-curing treatment may also be applied if desired. The organic polymer composition of the present invention is cured by exposing the composition to a temperature higher than about 250°C to about 500°C, more preferably about 350°C to about 450°C.

[0222] As discussed above, the compositions and methods described may be used to prepare underground tools and products used in applications within the petrochemical industry.

[0223] In final use, the glass transition temperature or higher operating temperature of crosslinked organic polymers varies depending on the material used. For crosslinked organic polymers, approximately 80°C to 300°C applies to crosslinked polyarylenes, approximately 180°C to 360°C to crosslinked polysulfones, approximately 200°C to 290°C to polyethersulfones, approximately 200°C to 380°C to polyimides, approximately 40°C to 100°C to polyamides, approximately -50°C to 260°C to polyureas, approximately -65°C to 100°C to polyurethanes, approximately 80°C to 130°C to polyphthalamides, approximately 200°C to 280°C to polyamideimides, approximately 180°C to 300°C to poly(benzimidazoles), and approximately 300°C to polyarylates. It has a glass transition temperature of approximately 180°C to 380°C, approximately 50°C to 160°C for LCP, and approximately 170°C to 250°C for polyaramid.

[0224] The information provided above may be used in various further embodiments described below, and each component may be as described in detail above. The elastomer material may be formed, for example, by heating a crosslinked aromatic polymer to its glass transition temperature or higher. In this embodiment, the aromatic polymer is crosslinked by reaction with the crosslinking compound and / or reactive crosslinking additive of this application, or by heat-induced crosslinking of the aromatic polymer grafted onto the aromatic polymer.

[0225] The elastomer articles described above may also be formed by thermoforming the compositions described above, which include a crosslinked aromatic polymer, to form a molded article, and the molded article may be heated to the glass transition temperature of the crosslinked aromatic polymer or a higher temperature. The aromatic polymer is crosslinked by reaction with the crosslinking compound of the present invention and / or the reactive crosslinking additive described above, or by thermally induced crosslinking of the aromatic polymer grafted to the aromatic polymer.

[0226] The elastomer material may be formed by preparing an aromatic polymer that is a non-elastomer at room temperature; and combining it with the crosslinking compound and / or crosslinking reaction additive of the present invention. The crosslinking compound and any crosslinking reaction additive (whether added independently or formed into oligomers) are then combined with the aromatic polymer to form a crosslinked aromatic polymer, which becomes an elastomer when heated to its glass transition temperature or higher.

[0227] Furthermore, embodiments including methods for using organic polymers in elastomer applications are within the scope of the present invention. Using the crosslinking compounds of this application, organic polymers are crosslinked to form a crosslinked organic polymer, which can be prepared using the heat-induced grafting technique of U.S. Patent No. 6,060,170. The crosslinked polymer is then heated to a temperature at or above its glass transition temperature during use, resulting in it becoming an elastomer. The crosslinked organic polymer may also be molded into an article, which is then placed in use, and as a result it is exposed to the heat applied to the article during use in a high-temperature end application, heating the crosslinked polymer to a temperature at or above its glass transition temperature to become an elastomer material.

[0228] In another embodiment of this application, the applicant describes herein compositions and methods suitable for manufacturing sealing components, seal connectors, and the like, which resist creep and extrusion and maintain good mechanical properties in end applications requiring high continuous operating temperatures and good chemical resistance as well. The applicant previously disclosed compositions and methods for manufacturing creep and extrusion-resistant sealing components in U.S. Patent No. 9,127,138. Such compositions were limited to certain crosslinking compounds that could be difficult and / or expensive to manufacture. Accordingly, the present invention provides compositions and methods for manufacturing creep and extrusion-resistant sealing components using a variety of crosslinking compounds that can be manufactured more easily and less cheaply.

[0229] The compositions described herein contain the crosslinked compounds of the present invention and are resistant to extrusion and creep while maintaining good sealing and ductility. The compositions are useful for forming sealing members, or sealing connectors and similar components used under harsh and / or high-temperature conditions. Where used herein, “high temperature” means its usual sense, and those skilled in the art will understand that a high-temperature environment includes those where the operating temperature is the glass transition temperature of the polymer in use or higher. With respect to the polymers discussed below, such a high-temperature environment typically exceeds 177°C (350°F). That is the case.

[0230] The composition comprises the aromatic polymers discussed above, as well as crosslinked compounds having the structures of formulas (I), (II), and (III), and may further include crosslinking reaction additives as desired. Crosslinking the composition allows for the formation of components with desired high-temperature properties. The crosslinking reaction here increases the glass transition temperature of the resulting product, resulting in better function and resistance to extrusion during use. The improved properties enable the use of the unfilled composition in high-temperature and / or harsh conditions, such as underground environments. This is a significant advantage in that the user does not need to fill the compound to help achieve the desired mechanical properties and resistance to creep during use. Instead, the user can maintain good mechanical properties and resistance to creep and extrusion while the sealing component maintains the desired ductility and tensile elongation of the seal that functions well in the ground.

[0231] The polymers used herein may be one or more known aromatic polymers and / or may be selected for high-temperature or creep-resistant use, and include polyarylene polymers, polysulfones, polyphenylene sulfides, polyimides, polyamides, polyureas, polyurethanes, polyphthalamides, polyamideimides, aramids, polybenzimidazoles, and their blends, copolymers, and derivatives. Preferably, the aromatic polymer is a polyarylene polymer and / or a polysulfone polymer, and its blends, copolymers, and derivatives. If the aromatic polymer is a polyarylene type polymer, it is preferably at least one of polyether ether ketone (PEEK), polyether ketone (PEK), polyether ketone ether ketone ketone (PEKEKK), polyether ketone ketone (PEKK), polysulfone (PSU), polyether sulfone (PES), polyaryl sulfone (PAS), and its blends, copolymers, and derivatives.

[0232] If the aromatic polymer is a polyarylene ether polymer, it may have repeating units of structure according to the structure of formula (XIII) discussed above. In a preferred embodiment, the organic polymer is a polyarylene ether having the structure according to formula (XIV) above.

[0233] When used with additives, the crosslinking compound can be reacted to form the reactive oligomerized crosslinking intermediate discussed above. The use of one or more crosslinking reaction additives can help to impart the much higher glass transition temperature and high crosslink density to the polymer discussed above.

[0234] The crosslinked composition and the organic polymer composition may also contain crosslinking reaction additives as needed. The crosslinking reaction additives include organic acids and / or acetate compounds that can promote the oligomerization of the crosslinked compounds, which are discussed in more detail above. Oligomerization can be carried out by the reactions shown and discussed above. The crosslinked composition has a weight percentage ratio of the crosslinked compound to the crosslinking reaction additives discussed above. Furthermore, the organic polymer composition has a weight percentage ratio of the organic polymer to the weight of the crosslinked compound, which are discussed above.

[0235] Compositions with extrusion resistance and creep resistance are preferably left unfilled, in particular in relation to strength additives that may affect ductility and tensile elongation. However, it is also within the scope of the present invention that organic polymer compositions may be further filled and / or strengthened and may contain one or more of the above additives to improve the modulus, impact strength, dimensional stability, heat resistance, and electrical properties of composites and other finished products formed using the polymer composition.

[0236] When producing an organic polymer composition, it is preferable to add the additive to the composition at the same time as, or almost simultaneously with, the time at which the crosslinking compound is combined with the organic polymer, in order to produce the organic polymer composition discussed above.

[0237] Furthermore, the organic polymer composition may further contain other compounding agents (e.g., plasticizers, stabilizers) as discussed above.

[0238] The thermoforming of the manufactured product may be carried out by any known or to be developed method in the art, as discussed above.

[0239] The compositions and / or methods described above may be used in or for applications in the petrochemical industry for underground tools and applications. In particular, the products are selected from the group consisting of acid-resistant coatings, chemical casting films, extruded films, solvent casting films, inflation films, encapsulated products, thermal insulation materials, packaging materials, composite cells, sealing connectors, and sealing assemblies with backing rings, packer elements, labyrinth seals for pumps, and MSE® seals with double-lip designs (available from Greene, Tweed & Co., Inc., Kulpsville), as well as other anti-extrusion and anti-creep components in the form of O-rings, V-rings, U-cups, gaskets, bearings, valve seats, adapters, wiper rings, V-shaped backing rings, and tubing.

[0240] The present invention also includes sealing components for sealing assemblies formed by a method comprising the step of crosslinking a composition described herein. A sealing connector having a sealing connector body formed by a method comprising the step of crosslinking a composition described herein is also included herein.

[0241] The present invention relates to a method for improving the extrusion and creep resistance of components used in high-temperature sealing elements or seal connectors, further comprising the steps of: preparing a composition comprising an aromatic polymer and a crosslinking compound having a structure selected from formulas (I), (II), and (III); and subjecting the composition to a thermoforming process to form a component and crosslinking the aromatic polymer described above. The composition is preferably not filled. The aromatic polymer and the crosslinking compound may be any of those described herein or above, and the composition may also contain crosslinking reaction additives as needed. [Examples]

[0242] (Example 1) Sample preparation A blend of the crosslinked compound of the present invention with an organic polymer and a crosslinking additive was prepared in a freeze mill. The blend was in powder form and has the formula: [ka] 3.4 grams of the crosslinking compound according to the present invention, PEEK (Vestakep 5000FP) The blend consisted of 16.6 grams of the polymer, 0.02 grams of a crosslinking additive, and lithium acetate dihydrate. A comparative sample containing only the polymer, PEEK (Vestakeep 5000FP), was also prepared. The inventive blend and the comparative sample were analyzed using differential scanning calorimetry (DSC) and parallel plate rheology to detect the presence of polymer crosslinking. These DSC and parallel plate rheology analyses clearly demonstrated that the inventive blend could induce thermal crosslinking. (Example 2) Differential scanning calorimetry

[0243] The invention blend and a comparative sample from Example 1 were analyzed to investigate crosslinking. Both the invention blend and the comparative sample were heated to a temperature of 500°C at a rate of 20°C / min during the first heating step. After heating, the samples were cooled to a temperature of 40°C at a rate of 5°C / min. Then, during the second heating step, the samples were heated to 400°C at a rate of 20°C / min. Graphs obtained as a result of the heat flow at each temperature during the second heating step are shown in Figure 5. The glass transition temperature of the PEEK comparative sample showed a glass transition temperature of 153°C. The second heating step for the invention blend showed a glass transition temperature of 160°C. The higher glass transition temperature of the invention blend containing PEEK compared to the PEEK-only comparative sample provides a strong indication that the invention blend underwent crosslinking of DSC cells. (Example 3) Rheology The sample from Example 1 was examined using an oscillator rheometer. Strain oscillation was applied to tablets of the inventive blend and the comparative sample in a parallel plate configuration. The rheological experiment was performed under a nitrogen atmosphere, with a strain of 0.1%, isothermal at 380°C, and a frequency of 1 Hz. The instrument was heated to 380°C, and then the sample was introduced. After the sample was inserted, the temperature was maintained at 380°C, and the storage modulus (G') and loss modulus (G'') were recorded for 30 minutes. The storage modulus represents the solid response of the material, and the loss modulus represents the viscous behavior. Therefore, if G' is less than G'', the material is in a viscous liquid state, but if G' is greater than G'', the material is solid, having exceeded its gelation point. If the polymer is crosslinked, the material transitions from a liquid state to a solid state where G' is greater than G''. Referring to Figure 6, the resulting rheological time sweep at 380°C for the comparative sample and the inventive blend is shown. For the comparative sample, the loss modulus (G”) was always greater than the storage modulus (G'), indicating that the comparative sample did not undergo crosslinking at 380°C and remained in a fluid state as a polymer molten material, which is typical for thermoplastic materials. In contrast, the inventive blend consistently showed a storage modulus (G') greater than the loss modulus (G”). This indicates that the inventive blend underwent rapid crosslinking at 380°C and remained in a solid state.

[0244] According to a preferred embodiment of the present invention, for example, the following is provided: (Section 1) A crosslinking composition comprising a crosslinking compound for crosslinking an organic polymer, wherein the crosslinking compound is [ka] Selected from the group consisting of, where Q is a bond, A is an alkyl, aryl, or arene moiety having a molecular weight of less than approximately 10,000 g / mol, and R 1 、R 2 and R 3 Each of them has a molecular weight of less than approximately 10,000 g / mol, R 1 、R 2 and R 3 They are the same or different, hydrogen, hydroxyl (-OH), amine (-NH). 2 ), selected from the group consisting of halides, ethers, esters, amides, aryls, arenes, or branched or linear saturated or unsaturated alkyl groups with 1 to about 6 carbon atoms, where m is 0 to 2, n is 0 to 2, m+n is greater than 0 or equal to 0 and less than 2 or equal to 2, Z is selected from the group consisting of oxygen, sulfur, nitrogen, and branched or linear saturated or unsaturated alkyl groups with 1 to about 6 carbon atoms, where x is about 1.0 to about 6.0. Crosslinking composition. (Section 2) The aforementioned crosslinked compound has the structure of formula (I), and the following

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Claims

[Claim 1] The invention as shown in the drawings.

Images