阅读说明：本技术 用于输送烃流体的热塑性硫化橡胶导管 (Thermoplastic vulcanizate conduit for transporting hydrocarbon fluids ) 是由 A·A·塔卡克斯 W·王 A·K·多法斯 K·安娜塔纳雷纳耶尔 D·N·维兰 K·I·多诺 于 2018-09-14 设计创作，主要内容包括：导管,特别是柔性导管包含管状内壳体、至少部分地围绕所述内壳体设置的至少一个增强层、至少部分地围绕所述至少一个增强层设置的外保护性护套、和任选的在所述至少一个增强层和所述外保护性护套之间设置的热绝缘层。所述外保护性护套和热绝缘层中的至少一个包含热塑性硫化橡胶组合物。(A catheter, in particular a flexible catheter, comprises a tubular inner housing, at least one reinforcement layer disposed at least partially around the inner housing, an outer protective sheath disposed at least partially around the at least one reinforcement layer, and optionally a thermal insulation layer disposed between the at least one reinforcement layer and the outer protective sheath. At least one of the outer protective sheath and the thermal insulation layer comprises a thermoplastic vulcanizate composition.)

1. A flexible catheter, comprising:

(a) an inner housing;

(b) at least one reinforcement layer disposed at least partially around the inner housing;

(c) an outer protective sheath disposed at least partially around the at least one reinforcing layer; and

(d) a thermal insulation layer disposed between the at least one reinforcing layer and the outer protective sheath,

wherein the thermal insulation layer comprises a thermoplastic vulcanizate composition comprising: (i) comprising at least one C derived from₄-C₇A dispersed phase of an at least partially cured rubber of repeating units of an isomonoolefin monomer and (ii) a continuous phase comprising at least one thermoplastic polymer.

2. The flexible conduit of claim 1, wherein the at least partially cured rubber of the dispersed phase comprises rubber derived from at least one C₄-C₇Repeating units of a multiolefin monomer.

3. The flexible conduit of claim 2, wherein the isomonoolefin comprises isobutylene and the multiolefin comprises para-methyl-styrene.

4. The flexible conduit of claim 2, wherein the isomonoolefin comprises isobutylene and the multiolefin comprises isoprene.

5. The flexible conduit of any preceding claim, wherein the rubber of the dispersed phase is halogenated.

6. The flexible conduit of claim 5, wherein the rubber is halogenated with bromine or chlorine (chloride).

7. The flexible catheter of any of claims 1-4, wherein the rubber of the dispersed phase is non-halogenated.

8. The flexible conduit of any preceding claim, wherein the dispersed phase of rubber is cured with a curing agent selected from at least one of: peroxides, phenolic curing agents, moisture curing agents, hydrosilylation curing agents, silane-based curing agents, and combinations thereof.

9. The flexible conduit of any preceding claim, wherein the continuous phase comprises at least one of polypropylene, polyethylene, and combinations thereof.

10. The flexible catheter of any of the preceding claims, wherein the continuous phase comprises a polyamide.

11. The flexible catheter of any of the preceding claims, wherein the thermoplastic vulcanizate composition comprises from about 30% to about 95% of dispersed phase (i) based on the total weight of the thermoplastic vulcanizate composition.

12. The flexible conduit of any preceding claim, wherein the thermoplastic vulcanizate composition comprises from about 5% to about 70% continuous phase (ii), based on the total weight of the thermoplastic vulcanizate composition.

13. The flexible conduit of any preceding claim, wherein the thermal insulation layer further comprises a filler.

14. The flexible conduit of any preceding claim, wherein the thermal insulation layer has at least one of the following properties:

(i) a thermal conductivity in the range of about 0.10 to about 0.20W/(m-K); and

(ii) an abrasion resistance of less than about 3% weight loss based on the total weight of the layer.

15. The flexible catheter of any of the foregoing claims 1-14, wherein the outer protective sheath comprises a second thermoplastic vulcanizate composition that is the same as the thermal insulation layer.

16. The flexible catheter of any of claims 1-14, wherein the outer protective sheath comprises a second thermoplastic vulcanizate composition comprising (i) a dispersed phase of ethylene-a-olefin-vinyl norbornene rubber that has been at least partially cured by hydrosilylation and (ii) a continuous phase comprising at least one second thermoplastic polymer.

17. The flexible catheter of any one of claims 1-14, wherein the outer protective sheath comprises a second thermoplastic vulcanizate composition and flexible catheter is compliant with at least one of API Spec17J, API Spec 17K, and DNV RP F119.

18. The flexible conduit of any preceding claim, wherein the thermal insulation layer and flexible conduit conform to at least one of API Spec17J, API Spec 17K, and DNV RP F119.

19. The flexible conduit of any preceding claim, wherein the curing agent is a phenolic resin.

20. The flexible conduit of claim 19, wherein the phenolic resin is a phenol-in-oil resin.

21. The flexible conduit of any of claims 1-14 and 18-20, wherein the thermoplastic vulcanizate composition comprises at least one oil.

22. The flexible conduit of claim 21, wherein the at least one oil is at least one of a paraffinic oil, a polyisobutylene, and combinations thereof.

23. The flexible catheter of claim 22, wherein the polyisobutylene has a number average molecular weight (M) of less than 10,000g/mol_n)。

24. The flexible conduit of any of claims 1-14 and 18-23, wherein the thermoplastic vulcanizate composition has a hardness in a range of from 60 shore a to 60 shore D.

25. The flexible conduit of any of claims 1-14 and 18-24, wherein the thermoplastic vulcanizate composition has a creep time of greater than 500 seconds.

26. The flexible conduit of any of claims 1-14 and 18-25, wherein the thermoplastic vulcanizate composition has a creep time of greater than 1000 seconds.

27. The flexible conduit of any of claims 1-14 and 18-26, wherein the thermal insulation layer has a wall thickness in a range of 0.5mm to 150 mm.

28. A flexible catheter, comprising:

(a) an inner housing;

(b) at least one reinforcement layer disposed at least partially around the inner housing; and

(c) an outer protective sheath disposed at least partially around the at least one reinforcing layer,

wherein the outer protective sheath comprises a thermoplastic vulcanizate composition comprising: (i) a dispersed phase of a rubber selected from the group consisting of: ethylene-alpha-olefin-vinyl norbornene, copolymers of ethylene-alpha-olefin with vinyl norbornene, and ethylene-alpha-olefin copolymers, and (ii) a continuous phase comprising at least one thermoplastic polymer.

29. The flexible conduit of claim 28, wherein the curing agent is selected from at least one of: peroxides, phenolic curing agents, moisture curing agents, hydrosilylation curing agents, silane-based curing agents, and combinations thereof.

30. The flexible catheter of any one of claims 28 and 29, wherein the dispersed phase comprises polypropylene.

31. The flexible catheter of any of claims 28-30, wherein the at least one thermoplastic polymer of the continuous phase comprises isotactic polypropylene.

32. The flexible conduit of any one of claims 28-31, wherein the at least one thermoplastic polymer of the continuous phase comprises polyethylene.

33. The flexible catheter of any one of claims 28-32, wherein the thermoplastic vulcanizate composition comprises from about 30% to about 95% of the dispersed phase (i) based on the total weight of the thermoplastic vulcanizate composition, and the thermoplastic vulcanizate composition comprises from 5% to 70% of the continuous phase (ii) based on the total weight of the thermoplastic vulcanizate composition.

34. The flexible catheter of any of claims 28-33, further comprising a thermal insulation layer, wherein the thermal insulation layer is between the at least one reinforcing layer and the outer protective sheath.

35. The flexible conduit of claim 34, wherein the thermal insulation layer comprises a second thermoplastic vulcanizate composition comprising: (i) comprising at least one C derived from₄-C₇A dispersed phase of an at least partially cured rubber of repeating units of an isomonoolefin monomer and (ii) a continuous phase comprising at least one thermoplastic polymer.

36. The flexible catheter of claim 34, wherein the thermal insulation layer comprises the same second thermoplastic vulcanizate composition as the outer protective sheath.

37. The flexible conduit of any one of claims 34-36, wherein the thermal insulation layer and flexible conduit conform to at least one of API Spec17J, API Spec 17K, and DNV RP F119.

38. The flexible catheter of any one of the preceding claims, wherein the outer protective sheath layer and flexible catheter conform to at least one of API Spec17J, API Spec 17K, and DNV RP F119.

39. The flexible conduit of any of claims 28-34 and 38, wherein the curing agent is a phenolic resin.

40. The flexible conduit of claim 39, wherein the phenolic resin is a phenol-in-oil resin.

41. The flexible conduit of any of claims 28-34 and 38-40, wherein the thermoplastic vulcanizate composition comprises at least one oil.

42. The flexible conduit of claim 41, wherein the at least one oil is at least one of a paraffinic oil, a polyisobutylene, and combinations thereof.

43. The flexible catheter of any one of claims 42, wherein the polyisobutylene has a number average molecular weight (M) of less than 10.000g/mol_n)。

44. The flexible conduit of any of claims 28-34 and 38-43, wherein the thermoplastic vulcanizate composition has a hardness in the range of 60 Shore A to 60 Shore D.

45. The flexible conduit of any of claims 28-34 and 38-44, wherein the thermoplastic vulcanizate composition has a creep time of greater than 500 seconds.

46. The flexible conduit of any of claims 28-34 and 38-45, wherein the thermoplastic vulcanizate composition has a creep time of greater than 1000 seconds.

47. The flexible catheter of any of claims 28-34 and 38-46, wherein the outer protective sheath has a wall thickness in a range of 0.5mm to 150 mm.

48. A catheter, comprising:

(a) an inner housing;

(b) at least one reinforcement layer disposed at least partially around the inner housing; and

(c) an outer protective sheath disposed at least partially around the at least one reinforcing layer,

wherein the outer protective sheath comprises a thermoplastic vulcanizate composition comprising: (i) a dispersed phase of a rubber component comprising a butyl rubber that has been at least partially cured with a curative, the butyl rubber being selected from the following: isobutylene-isoprene rubber (IIR), bromoisobutylene-isoprene rubber (BIIR), brominated isobutylene p-methyl-styrene terpolymer rubber (BIMSM), and any combination thereof, and (ii) a continuous phase of a thermoplastic component.

49. The catheter of claim 48, wherein the catheter is manufactured by a manufacturing method selected from the group consisting of: extrusion, coextrusion, blow molding, injection molding, thermoforming, elastic welding, compression molding, 3D printing, pultrusion, and any combination thereof.

50. The catheter of any one of claims 48-49, wherein the outer protective sheath and catheter conform to at least one of APISpec 17J, API Spec 17K, and DNV RP F119.

51. A catheter, comprising:

(a) an inner housing;

(b) at least one reinforcement layer disposed at least partially around the inner housing;

(c) an outer protective sheath disposed at least partially around the at least one reinforcing layer; and

(d) a thermal insulation layer disposed between the at least one reinforcing layer and the outer protective sheath,

wherein the thermal insulation layer comprises a thermoplastic vulcanizate composition comprising: (i) a dispersed phase of a rubber component comprising a butyl rubber that has been at least partially cured with a curative, the butyl rubber being selected from the following: isobutylene-isoprene rubber (IIR), bromoisobutylene-isoprene rubber (BIIR), brominated isobutylene p-methyl-styrene terpolymer rubber (BIMSM), and any combination thereof, and (ii) a continuous phase of a thermoplastic component.

52. The conduit of claim 50 wherein the conduit is manufactured by a manufacturing process selected from the group consisting of: extrusion, coextrusion, blow molding, injection molding, thermoforming, elastic welding, compression molding, 3D printing, pultrusion, and any combination thereof.

53. The catheter of any one of claims 50-51, wherein the thermal insulation layer and catheter conform to at least one of API Spec17J, API Spec 17K, and DNV RP F119.

Brief description of the drawings

Fig. 1 is a cross-sectional view of a catheter according to one or more embodiments of the present disclosure.

Fig. 2 is a view of a catheter according to one or more embodiments of the present disclosure.

Figure 3 is a graph showing the relationship between propylene content and thermal conductivity of a TPV composition according to one or more embodiments of the present disclosure.

Figure 4 is a graph showing the relationship between propylene content and creep time for a TPV composition according to one or more embodiments of the present disclosure.

Detailed description of the embodiments

The present disclosure relates to conduits for the transport of hydrocarbon fluids (and related fluids), and particularly, but not exclusively, hydrocarbon fluids from oil and gas production facilities. Such conduits may be used, for example, for transporting fluids between a hydrocarbon reservoir and an offshore platform for the separation of oil, gas and water components. It has been found that certain specific thermoplastic vulcanizate (TPV) compositions exhibit excellent properties for use as thermal insulation layers, including where such layers additionally serve as an outer protective layer or jacket for conduits for the transport of hydrocarbon fluids.

In the present disclosure, the terms "conduit," "pipe," "hose," "tube," and the like may be used interchangeably. In addition, the terms "shell", "jacket" and "layer" may be used interchangeably in the practice of the present invention. The conduit described herein comprises at least a tubular inner casing (which in use is in contact with a hydrocarbon fluid being conveyed), at least one reinforcing layer disposed at least partially around the inner casing, and an outer protective sheath disposed at least partially around the at least one reinforcing layer. The various layers of such conduits are required to have different and exact properties, and depending on these properties are currently formed from several polymer components and metal components.

The tubular inner casing provides a passage for the flow of hydrocarbon fluids (such as oil and/or gas, and other fluids mixed therewith, such as water, production fluids, etc.) and must therefore exhibit certain qualities, including for example gas tightness and chemical resistance. In some cases, the inner tube housing provides the flexible nature of a flexible conduit and may be folded in a given direction under an external pressure greater than the pressure within the conduit. The reinforcement layer provides conduit integrity and structure to withstand the pressure applied to the pipe without causing irreversible damage to the conduit. That is, the reinforcement layer imparts strength to the catheter and may be composed of, for example, one or more sheets (laminae) or layers of metal, reinforced polymer (e.g., carbon nanotube reinforced polyvinylidene fluoride (PVDF)), and the like, and combinations thereof. Examples of tubular inner housings and reinforcing layers are described in U.S. patent nos. 6,679,298, 6,123,114, 3,687,169 and 9,090,019, which are fully incorporated herein by reference. An outer protective sheath (or simply "outer sheath") provides protection against the external environment, such as against wear and fatigue applied to the catheter. The outer protective sheath may be comprised of a polymeric material that thus imparts, among other qualities, abrasion and fatigue resistance to the catheter.

The other layers may additionally form part of the conduit, as described in more detail below, and each layer may be composed of or have a polymer component adjacent thereto. Thus, these polymer components must exhibit physical requirements for resistance to fluid exposure, chemical reactivity, heat transfer, abrasion and aging, as well as pressure, temperature and mechanical stress to meet chemically challenging environments. The polymeric component that imparts thermal insulation is particularly important for inclusion in such catheters. Failure to properly thermally insulate conduits, particularly those used at extreme temperatures, may allow hydrate plugs (i.e., crystalline solids) to form, which may restrict flow within the conduits, damage equipment, and potentially compromise the safety of production and/or personnel of the oil and gas operation. Indeed, it is estimated that the prevention of hydrate plugs formation and their removal represents approximately 70% of deepwater oil and gas flow safety challenges.

Thermoplastic materials such as polyolefins, polyamides, engineering thermoplastics (e.g., PVDF), and composite polypropylene (PP) foams are currently commonly used as thermal insulation layers in the conduits for hydrocarbon fluid transport described herein. Such materials may have various limitations. For example, syntactic PP foam is a commonly used thermal insulation material for conduits, having an initial thermal conductivity of 0.16 watts per meter kelvin (W/mK). However, when the catheter and, in turn, the composite PP material included in the catheter are exposed to various operating conditions such as pressure and extreme temperatures, the thermal conductivity quality decreases. To compensate, the composite PP material must be over engineered to last the duration of the catheter life (e.g., 20 or 30 years), thereby resulting in larger, thicker, and heavier catheters.

It has now been found that certain thermoplastic vulcanizate (TPV) compositions provide an attractive alternative to current materials for certain catheter components. TPV compositions exhibit low thermal conductivity and durability over the life of the catheter, thereby allowing the use of thinner (e.g., reduced outer diameter) and lighter catheters and achieving a reduction in associated costs.

One or more illustrative embodiments comprising embodiments of the disclosure are included and presented herein. In the interest of clarity, not all features of a physical implementation are necessarily described or shown in this application. It will be appreciated that in the development of a physical embodiment that comprises an embodiment of the present disclosure, numerous implementation-specific decisions must be made in order to achieve the developer's goals, such as compliance with system-related, business-related, government-related, and other constraints, which will vary from one implementation to another. While a developer's efforts might be time-consuming, such efforts would be, nevertheless, a routine undertaking for those of ordinary skill in this art having the benefit of this disclosure.

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as physical properties, reaction conditions, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the embodiments of the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Where the term "less than about" or "greater than about" is used herein, the modified amount includes the recited amount, thereby including a value of "equal to". That is, "less than about 3.5%" as used herein includes a value of 3.5%.

Although compositions and methods are described herein in terms of "comprising" various components or steps, the compositions and methods can also "consist essentially of" or "consist of" the various components and steps.

Various terms used herein are defined below. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in one or more printed publications or issued patents.

Thermoplastic vulcanizate composition

As used herein, the term "thermoplastic vulcanizate" (also referred to herein simply as "TPV") and grammatical variations thereof is defined broadly as any material that includes (i) a dispersed phase of rubber that has been at least partially cured and (ii) a continuous phase that includes at least one thermoplastic component (e.g., a polyolefin thermoplastic resin). The TPV material may also include other ingredients, other additives, or combinations thereof.

The term "vulcanized rubber" and grammatical variations thereof refer to compositions that include some components (e.g., rubber) that have been vulcanized. The term "vulcanized" and grammatical variations thereof are defined herein as compositions in which all or a portion of the composition (e.g., a crosslinkable rubber) has been subjected to a degree or amount of vulcanization. Thus, the term includes both partial and full cures. The preferred type of vulcanization is "dynamic vulcanization" discussed below, which also produces a "vulcanizate". Further, in at least one specific embodiment, the term cured refers to more than insubstantial curing (e.g., curing (or crosslinking)) that results in a measurable change in the relevant property (e.g., a 10% or more change in the composition Melt Flow Index (MFI) according to any ASTM-1238 procedure). In at least one or more contexts, the term cure includes both any form of curing (or crosslinking), thermal or chemical, that can be used in dynamic vulcanization.

The term "dynamic vulcanization" and grammatical variations thereof refers to the vulcanization or curing of a curable rubber blended with a thermoplastic component (e.g., a thermoplastic resin component) under shear conditions at a temperature sufficient to plasticize the mixture. In at least one embodiment, the rubber component is simultaneously crosslinked and dispersed as micron-sized particles within the thermoplastic component. Depending on the degree of curing, the ratio of rubber to thermoplastic component, the compatibility of the rubber component and the thermoplastic component, the type of kneader and the intensity of mixing (shear rate), other morphologies (e.g. co-continuous rubber phase in the plastic matrix) are possible.

As used herein, the term "partially vulcanized" and grammatical variations thereof (e.g., "at least partially vulcanized") with respect to a rubber component is a rubber component in which greater than 5 weight percent (wt.%) of the rubber component (e.g., the crosslinkable rubber component) is extractable in boiling xylene after vulcanization, preferably dynamic vulcanization (e.g., crosslinking of the rubber phase of a thermoplastic vulcanizate). For example, at least 5 wt.% and less than 20 wt.%, or less than 30 wt.%, or less than 50 wt.% of the rubber component may be extractable from a sample of the thermoplastic vulcanizate in boiling xylene, including any values and subsets therebetween. The percentage of extractable rubber can be determined by techniques set forth in U.S. Pat. No. 4,311,628, which is incorporated herein by reference in its entirety.

Rubber component

The rubber component of the TPVs described herein for use in the catheters of the present disclosure may be any material recognized by those skilled in the art as "rubber," preferably a cross-linkable rubber component (e.g., prior to vulcanization) or a cross-linked rubber component (e.g., after vulcanization). That is, the rubber that may be used to form the rubber component (phase) of the TPV compositions used in the catheters described herein may include any polymer that is capable of curing or crosslinking. It is mentioned that the rubber component may comprise a mixture of more than one rubber. Non-limiting examples of rubbers may include olefinic elastomeric copolymers, butyl rubbers, and mixtures thereof. In one or more embodiments, the olefinic elastomeric copolymer may include, but is not limited to, an ethylene-propylene-non-conjugated diene rubber or a propylene-based rubber copolymer containing units derived from non-conjugated diene monomers. In some embodiments, the rubber component may be an ethylene-propylene copolymer (EPM), including saturated compounds, which may be vulcanized using free radical generating agents such as organic peroxides (as described in U.S. patent No. 5,177,147, which is incorporated herein by reference in its entirety) or other curing systems. Thus, the rubber component can include, but is not limited to, ethylene-propylene diene monomer rubber (EPDM) or EPDM type rubber, e.g., the EPDM type rubber can be a terpolymer derived from the polymerization of at least two different monoolefin monomers having from 2 to 10 carbon atoms, preferably from 2 to 4 carbon atoms, and at least one polyunsaturated olefin having from 5 to 20 carbon atoms, including any value or subset therebetween.

As used herein and unless otherwise specified, the term "copolymer" and grammatical variations thereof refers to a polymer (e.g., terpolymer, tetrapolymer, etc.) derived from two or more monomers.

The term "ethylene-propylene rubber" and grammatical variations thereof refers to a rubbery copolymer polymerized from ethylene, propylene, and at least one diene monomer. The diene monomer may include, but is not limited to, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, divinylbenzene, 1, 4-hexadiene, 5-methylene-2-norbornene, 1, 6-octadiene, 5-methyl-1, 4-hexadiene, 3, 7-dimethyl-1, 6-octadiene, 1, 3-cyclopentadiene, 1, 4-cyclohexadiene, dicyclopentadiene, and any combination thereof. As will be discussed in more detail below, in certain embodiments, it is worth noting that in preparing the TPV compositions used in the outer protective sheath or thermal insulation layer of the catheters described herein, the rubber component may comprise an ethylene-a-olefin-vinyl norbornene rubber.

The ethylene-propylene rubber may comprise from about 40 to about 85 weight percent (wt.%), or from about 50 to about 70 wt.%, or from about 60 to about 66 wt.% of units derived from ethylene, based on the total weight of ethylene and propylene in the rubber, including any values and subsets therebetween. Additionally, the ethylene-propylene rubber may contain from about 0.1 to about 15 weight percent, or from about 0.5 to about 12 weight percent, or from about 1 to about 10 weight percent, or from about 2 to about 8 weight percent of units derived from diene monomer, including any values and subsets therebetween. Expressed in mole percent, the ethylene-propylene rubber may comprise from about 0.1 to about 5 mole percent, or from about 0.5 to about 4 mole percent, or from about 1 to about 2.5 mole percent of units derived from a diene monomer, including any values and subsets therebetween. In one or more embodiments in which the diene comprises 5-ethylidene-2-norbornene, the ethylene-propylene rubber may comprise at least 1 weight percent, or at least 3 weight percent, or at least 4 weight percent, or at least 5 weight percent, or from about 1 to about 15 weight percent, or from about 5 weight percent to about 12 weight percent, or from about 7 weight percent to about 11 weight percent of units derived from 5-ethylidene-2-norbornene, including any values and subsets therebetween. In one or more embodiments in which the diene includes 5-vinyl-2-norbornene, the ethylene-propylene rubber may include at least 1 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or from about 1 to about 15 wt%, or from about 5 wt% to about 12 wt%, or from about 7 wt% to about 11 wt% of units derived from 5-vinyl-2-norbornene, including any values and subsets therebetween.

The ethylene-propylene rubber may have a weight average molecular weight (M) in the range of 100,000 g/mole to 1,200,000 g/mole_w) Bag (bag)Including any values and subsets therebetween. M_wMay be greater than 100,000 g/mole, or greater than 200,000 g/mole, or greater than 400,000 g/mole, or greater than 600,000 g/mole. Preferably, M of ethylene-propylene rubber_wLess than 1,200,000 g/mole, or less than 1,000,000 g/mole, or less than 900,000 g/mole, or less than 800,000 g/mole.

Suitable ethylene-propylene rubbers may have a number average molecular weight (M) in the range of 20,000 g/mole to 500,000 g/mole_n) Including any values and subsets therebetween. M_nMay be greater than 20,000 g/mole, or greater than 60,000 g/mole, or greater than 100,000 g/mole, or greater than 150,000 g/mole, including any values and subsets therebetween. M of ethylene-propylene rubber_nMay be less than 500,000 g/mole, or less than 400,000 g/mole, or less than 300,000 g/mole, or less than 250,000 g/mole.

For determining molecular weight (M)_n、M_wAnd M_z) And Molecular Weight Distribution (MWD) techniques can be found in U.S. Pat. No. 4,540,753, which is incorporated herein by reference in its entirety, and Macromolecules, 1988, volume 21, page 3360, to vermate et al (using polystyrene standards, which are also incorporated herein by reference in their entirety).

The ethylene-propylene rubber used herein may also pass the Mooney viscosity (ML) in accordance with ASTM D-1646₍₁₊₄₎At 125 ℃) from about 10 to about 500, or from about 50 to about 450, including any values and subsets therebetween.

In some embodiments, the ethylene-propylene rubber may be characterized by an intrinsic viscosity (as measured in decalin at 135 ℃ in accordance with ASTM D-1601) of from about 1 to about 8 deciliters per gram (dl/g), or from about 3 to about 7dl/g, or from about 4 to about 6.5dl/g, including any values and subsets therebetween.

In some embodiments, the ethylene-propylene rubber used herein in the catheters of the present disclosure may have a glass transition temperature (T) of less than-20 ℃, in other embodiments less than-30 ℃, in other embodiments less than-50 ℃, and in other embodiments from about-20 to about-60 ℃_g) By differential scanning calorimetryMethod (DSC) was determined according to ASTM E-1356 using a heating/cooling rate of 10 ℃/min.

Suitable ethylene-propylene rubbers may be manufactured or synthesized by using a variety of techniques. For example, they can be synthesized by using solution, slurry or gas phase polymerization techniques employing various catalyst systems. Exemplary catalysts include, but are not limited to, Ziegler-Natta systems such as those including vanadium catalysts, and single-site catalysts including constrained geometry catalysts involving group IV-VI metallocenes. Elastomeric copolymers are available under the trade name VISTALON^TM(available from ExxonMobil Chemical Company, Houston, Tex.), KELTAN^TM(available from Lanxess corporation, Pittsburgh, Pa.), NORDEL IP^TM(available from Dow Chemical Company, Midland, Mich.), Nordel MG^TM(available from Dow Chemical Company, Midland, Mich.), ROYALENE^TM(available from Leishma Lion Elastomers, Louisiana) and BUNA^TMCommercially available (available from Lanxess corporation, Pittsburgh, Pa.).

In certain embodiments, it is preferred that in preparing a TPV composition for use in the outer protective jacket thermal insulation layer, the rubber component may comprise an ethylene-a-olefin-vinyl norbornene rubber. Suitable alpha-olefins include, but are not limited to, propylene, 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and any combination thereof. In some embodiments, it is preferred that in preparing the TPV composition for use in the outer protective sheath, the rubber component is one or more of the following: ethylene-alpha-olefin-vinyl norbornene, copolymers of ethylene-alpha-olefin and vinyl norbornene, and/or ethylene-alpha-olefin copolymers that have been at least partially cured with a curing agent.

In some embodiments, it is preferred that in preparing the TPV used in the barrier layer, the rubber component may be butyl rubber. The term "butyl rubber" and grammatical variations thereof include polymers comprising predominantly repeat units from isobutylene and also comprising repeat units of a minor amount of a monomer that provides a crosslinking site. Monomers that provide crosslinking sites may include, but are not limited to, polyunsaturated monomers such as conjugated dienes or divinyl benzene. In one or more embodiments, the butyl rubber polymer may be halogenated to further enhance the crosslinking reactivity, which is referred to herein as "halogenated butyl rubber".

The rubber component may be, for example, homopolymers of conjugated dienes having from 4 to 8 carbon atoms and rubber copolymers having at least 50 weight percent of repeating units derived from at least one conjugated diene having from 4 to 8 carbon atoms, including any values and subsets therebetween.

In some embodiments, it is worth noting that in preparing a TPV composition for use in an outer protective jacket or thermal insulation layer, the rubber component may comprise a rubber derived from at least one C₄-C₇Repeating units of an isomonoolefin monomer (e.g., isobutylene). In a preferred embodiment, the thermal insulation layer comprising the TPV composition described herein has a rubber component comprising a rubber derived from at least one C₄-C₇Repeating units of an isomonoolefin monomer (e.g., isobutylene). In other embodiments, the rubber component may comprise a rubber derived from at least one C₄-C₇Repeat units of isomonoolefin monomers and derived from at least one C₄-C₇Repeating units of multiolefin monomers such as isoprene and p-methylstyrene. Preferably, para-methylstyrene is a multiolefin monomer. Preferably, the rubber is halogenated, for example, using bromine or chlorine. Suitable polymers for the rubber component include, but are not limited to, those sold under the trade name EXXPRO^TMSpecial Elastomers brominated isobutylene p-methyl-styrene terpolymer commercially available from ExxonMobil Chemical Company under the trade name EXXON^TMBromobutyl 2244、EXXON^TMBromobutyl 2255 and EXXON^TMButyl and halogenated Butyl polymers, Butyl268 commercially available from ExxonMobil Chemical Company, and sold X _ BUTYL^TMAnd Regular X _ BUTYL^TMBrominated isobutylene-isoprene copolymers are commercially available from Arlanxeo Holding b.v.

In some embodiments, comprises C₄-C₇Isomonoolefin monomer orC₄-C₇Isomonoolefin monomers with monomers derived from at least one C₄-C₇The rubber phase of repeating units of the multiolefin monomer may be present in the TPV composition in the outer protective jacket and/or the thermal insulation layer. In some embodiments, the thermal insulation layer and the outer protective sheath are the same layer or different layers of the catheter, as described herein. In some embodiments, there may be more than one thermal insulation layer in various portions of the catheter, which may or may not include an outer protective sheath, without departing from the scope of the present disclosure.

Thus, the rubber component used in one or more layers of the catheter of the present disclosure (e.g., one or more thermal insulation layers and/or an outer protective sheath) may comprise one or more of EPDM rubber, isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), and/or brominated isobutylene p-methylstyrene terpolymer rubber (BIMSM). In some embodiments, the rubber component is preferably crosslinked. Examples of suitable commercially available crosslinked rubbers for use in embodiments of the present disclosure include, but are not limited to, those under the tradename EXXPRO^TM(e.g., EXXPRO)^TM3745) Brominated copolymers of isobutylene and para-methylstyrene (available from ExxonMobil Chemical Company, Houston, Tex.).

The rubber may be at least partially or fully cured by using dynamic vulcanization techniques. The rubber component may be vulcanized under conditions of shear and stretching at a temperature at or above the melting point of the thermoplastic component in the TPV. The rubber component is preferably simultaneously crosslinked and dispersed (preferably as fine particles) within the thermoplastic component matrix, but other morphologies such as co-continuous morphology may be present depending on the degree of cure, rubber to plastic viscosity ratio, mixing strength, residence time, temperature, and the like.

After dynamic vulcanization, the rubber component may be in the form of finely divided and well dispersed particles of vulcanized or cured rubber within a continuous thermoplastic component phase or matrix, although co-continuous morphology is also possible. In those embodiments in which the cured rubber is in the form of finely divided and well-dispersed particles within the thermoplastic medium, the rubber particles typically have an average diameter of less than 50 μm, or less than 30 μm, or less than 10 μm, or less than 5 μm, or less than 1 μm, each of which may have a lower limit of, for example, 0.1 μm, including any values and subsets therebetween. In a preferred embodiment, the rubber particles of the TPV composition have an average diameter in the range of 0.8 to 5 μm, including any values and subsets therebetween.

As described above, it is preferred to at least partially cure the rubber component used within the TPV compositions used in the catheters described herein (i.e., the outer protective sheath and/or the thermal insulation layer). In one or more embodiments, it may be advantageous to fully or fully cure the rubber. The degree of cure can be measured by determining the amount of rubber extractable from the thermoplastic vulcanizate by using cyclohexane or boiling xylene as an extractant. Preferably, the rubber has a degree of cure of no more than 15 wt.%, or no more than 10 wt.%, or no more than 5 wt.%, or no more than 3 wt.%, including 0 wt.%, extractable by cyclohexane at 23 ℃, as described in U.S. Pat. nos. 4,311,628, 5,100,947 and 5,157,081, which are all incorporated herein by reference in their entirety. Alternatively, the rubber may have a degree of cure such that the crosslink density is at least 4x10^-5Or at least 7x10^-5Or at least 10x10^-5Mol/ml rubber. See Crosslink definitions and Phase morphology Vulcanized TPEs, Rubber Chemistry and Technology, Vol.68, page 573-584 (1995), Ellul et al, which is incorporated herein by reference in its entirety.

The cure system used in dynamically vulcanizing the rubber component of the present disclosure is not considered to be particularly limiting. For example, the rubber component of the TPV composition may be cured by various curatives. As used herein, the term "curative" and grammatical variations thereof refers to any substance capable of curing or crosslinking the rubber component of the present disclosure. Examples of suitable curing agents include, but are not limited to, phenolic resins (e.g., novolac resins), metal oxides (e.g., ZnO, CaO, MgO, Al)₂O₃、CrO₃、FeO、Fe₂O₃NiO), stearic acid, and the like, and any combination thereof, hydrogenationSilylation (also known as silicon-containing curing systems, such as silane curing (hydrosiloxane curing)), free radical curing systems (such as peroxides), moisture curing after silane curing, and the like, and any combination thereof. In some embodiments, the curing agent is a phenolic resin or a hydrogen containing siloxane.

Useful phenolic curing systems are disclosed in U.S. Pat. nos. 2,972,600, 3,287,440, 5,952,425, and 6,437,030, which are incorporated herein by reference in their entirety. In one or more embodiments, the phenolic resin curing agent comprises a resole, which can be prepared by the condensation of an alkyl substituted phenol or unsubstituted phenol with an aldehyde, preferably formaldehyde, in an alkaline medium, or by the condensation of a difunctional phenolic diol. The alkyl substituent of the alkyl-substituted phenol can contain from 1 to about 10 carbon atoms, including any values and subsets therebetween.

Examples of phenolic resin curing agents include, but are not limited to, those defined according to formula a:

wherein Q is-CH₂-or-CH₂-O-CH₂-a divalent group of (a); m is zero or a positive integer from 1 to 20 and R' is an organic group. In one embodiment, Q is a divalent group-CH₂-O-CH₂-m is zero or a positive integer from 1 to 10 and R' is an organic group having less than 20 carbon atoms. In other embodiments, m is zero or a positive integer from 1 to 10 and R' is an organic group having from 4 to 12 carbon atoms.

The phenolic resin may be used in an amount of, for example, about 2 to about 6 parts by weight, or about 3 to about 5 parts by weight, or about 4 to about 5 parts by weight per 100 parts by weight of the rubber component, including any values and subsets therebetween.

The phenolic resin may be accompanied by a supplementary catalyst, such as stannous chloride (SnCl)₂). In some embodiments, the amount of stannous chloride may include from about 0.5 to about 2.0 parts by weight, or from about 1.0 to about 1.5 parts by weight, or from about 1.2 to about 1.3 parts by weight per 100 parts by weight of the rubber component, including any values and subsets therebetween. Is connected with itSuitably, about 0.1 to about 6.0 parts by weight, or about 1.0 to about 5.0 parts by weight, or about 2.0 to about 4.0 parts by weight of zinc oxide may also be used, including any values and subsets therebetween. In one or more embodiments, the olefinic rubber used with the phenolic curing agent includes diene units derived from 5-ethylidene-2-norbornene. In a preferred embodiment, the phenolic resin is dispersed in a paraffinic oil (e.g., pre-dispersed in an oil) (e.g., 70 wt% oil/30 wt% solid phenolic resin), which may be referred to herein as a "phenol-in-oil resin" or "RIO". Examples of suitable commercially available phenolic curing agents (e.g., a phenol-in-oil resin having 30 wt.% phenolic resin and 70 wt.% oil) include resole resins of schencladia SI Group, inc.

As used herein, "hydrosilylation" refers to the addition of silicon hydride across multiple bonds, often using a transition metal catalyst. Such curing agents are described in canadian patent No. 2190059 and U.S. patent No. 7,951,871, both of which are incorporated by reference herein in their entirety.

In certain embodiments, in preparing a TPV composition for use in an outer protective jacket and/or thermal insulation layer, the rubber phase may comprise an ethylene-a-olefin-vinyl norbornene rubber cured with a silicon-containing curing agent (i.e., a hydrosilation reaction). Useful silicon-containing curing agents include, but are not limited to, silicon hydride compounds having at least two SiH groups. These compounds react with the carbon-carbon double bonds of the unsaturated polymer in the presence of a hydrosilation catalyst. The silicon hydride compounds useful in embodiments described herein include, but are not limited to, methylhydrogenpolysiloxanes, methylhydrogendimethyl-siloxane copolymers, alkylmethylpolysiloxanes, bis (dimethylsilyl) alkanes, bis (dimethylsilyl) benzenes, and the like, and any combination thereof.

In some embodiments, the curing agent may be present in an amount of from 0.5phr to 20phr or from 0.5phr to 15phr, including any values and subsets therebetween. As used herein, the term "phr" refers to parts per hundred dry rubber (i.e., rubber without any oil) and is a measure of the components within the composition relative to the total weight of rubber, based on 100 parts by weight of rubber. Measurements in "phr" are units of measurement generally known to those skilled in the art.

In some embodiments, the rubber component (continuous phase) comprises 10 to 95 wt.%, or, e.g., 20 to 95 wt.%, or, e.g., 10 to 80 wt.%, such as 15 to 75 wt.%, or, e.g., 15 to 70 wt.%, or, e.g., 20 to 60 wt.%, including any values and subsets therebetween, of the total weight of the thermoplastic vulcanizate composition, including any additives. In some embodiments, the rubber component is present in the TPV compositions of the present disclosure in an amount of 20 to 95 wt.%, or 20 to 50 wt.%, including any values and subsets therebetween, of the total weight of the thermoplastic vulcanizate composition.

Thermoplastic phase

As used herein, the terms "thermoplastic component", "thermoplastic phase" or "thermoplastic polymer" and grammatical variations thereof of the thermoplastic vulcanizates of the present disclosure refer to any material that is not a "rubber" but a polymer or polymer blend that is considered by those skilled in the art to be thermoplastic in nature (e.g., a polymer that softens when exposed to heat and returns to its original state when cooled to room temperature). Each such term may be used interchangeably herein.

The thermoplastic component may include, for example, a thermoplastic polymer that is a solid, typically a high molecular weight plastic resin. Exemplary thermoplastic polymers include, but are not limited to, crystalline, semi-crystalline, and crystallizable polyolefins, olefin homopolymers and copolymers, non-olefin resins, and the like, and any combination thereof.

In embodiments, the thermoplastic component is a polymer including, but not limited to, polyamide resin(s) and mixtures thereof; particularly preferred resins include, for example, nylon 6, nylon 6/66 copolymer, nylon 11, nylon 12, nylon 610, nylon 612, and blends thereof. According to an alternative preferred embodiment of the present disclosure, the thermoplastic component is an elastomeric composition formulated using nylon 11 or a copolymer of nylon 12 and nylon 6/66 in a compositional ratio (weight ratio) of from about 10/90 to about 90/10, preferably from about 30/70 to about 85/15, including any values and subsets therebetween.

The thermoplastic component may comprise one or more polyolefins, including polyolefin homopolymers and polyolefin copolymers. In one or more embodiments, the polyolefin thermoplastic component comprises at least one of: i) polymers prepared from olefin monomers having 2 to 7 carbon atoms and/or ii) copolymers prepared from olefin monomers having 2 to 7 carbon atoms with (meth) acrylates or vinyl acetate. In some embodiments, the thermoplastic component may be formed by polymerizing ethylene or an alpha-olefin such as propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof. Ethylene and propylene and copolymers of ethylene and/or propylene with additional alpha-olefins such as 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and any combinations and copolymers thereof (e.g., with methacrylates and/or vinyl acetate). In some embodiments, the propylene-based polymer may also include units derived from the copolymerization of ethylene and/or an alpha-olefin, such as 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and any combination thereof.

In some embodiments, the thermoplastic component of the TPV composition may include propylene with ethylene or the higher α -olefins described above or with C₁₀-C₂₀Impact and/or random copolymers of dienes. The comonomer content of these propylene copolymers may range from about 1% to about 30% by weight of the polymer, including any values and subsets therebetween, for example, as described in U.S. patent No. 6,867,260, which is incorporated herein by reference in its entirety. Suitable commercially available thermoplastic components include those known under the trade name VISTA MAXX^TM(available from ExxonMobil Chemical Company, Houston, Tex., or VERSIFY available from Dow Chemical Company, Midland, Mich.)^TM) The olefinic elastomer of (1).

Other suitable polyolefin copolymers may include copolymers of olefins with styrene such as styrene-ethylene copolymers or polymers of olefins with α, β -unsaturated acids and/or α, β -unsaturated esters such as polyethylene-acrylate copolymers. The non-olefinic thermoplastic polymer may include, but is not limited to, polymers and copolymers of styrene, α, β -unsaturated acids, α, β -unsaturated esters, and any combination thereof. For example, polystyrene, polyacrylate and/or polymethacrylate may be used. Mixtures or blends (with or without other polymer modifiers) of two or more polyolefin thermoplastics such as those described herein are also suitable for use in the TPV composition embodiments described herein. Suitable thermoplastic polymers may also include impact and reactor copolymers.

In one or more embodiments, the thermoplastic component comprises polypropylene. As used herein, the term "polypropylene" and grammatical variations thereof broadly refers to any polymer that is considered "polypropylene" by one of skill in the art (as reflected in at least one patent or publication) and includes, but is not limited to, homo-, impact-and random polymers of propylene. In one or more embodiments, the thermoplastic component is or includes isotactic polypropylene. Preferably, the thermoplastic component contains one or more crystalline propylene homopolymers or copolymers of propylene having a melting temperature greater than 105 ℃ as measured by Differential Scanning Calorimetry (DSC). Preferred propylene copolymers include, but are not limited to, terpolymers of propylene, impact copolymers of propylene, random polypropylene copolymers, and any combination thereof. Preferred comonomers have 2 carbon atoms, or 4 to 12 carbon atoms. Preferably, the comonomer is ethylene. Such thermoplastic components and methods of making them are described in U.S. Pat. No. 6,342,565, which is incorporated herein by reference in its entirety. In one or more preferred embodiments, the polyolefin thermoplastic component comprises polyethylene, polypropylene, ethylene-propylene copolymers, and any combination thereof. In some embodiments, the thermoplastic component is a High Melt Strength (HMS) thermoplastic propylene, such as a high melt strength polypropylene (HMS-PP) and/or a high melt strength long chain branched polypropylene (HMS LCB-PP). In some embodiments, the thermoplastic propylene may be a polypropylene fractionated melt flow homopolymer ("fractionated PP"), alone or in combination with any other thermoplastic compound. In some embodiments, the plastic phase comprises a random copolymer or an impact copolymer polypropylene, or a combination thereof.

The thermoplastic component may comprise a propylene-based polymer, including solid, usually high molecular weight plastic resins, which contain predominantly units derived from the polymerization of propylene. In certain embodiments, at least 75%, or at least 90%, or at least 95%, or at least 97%, including up to 100%, of the units of the propylene-based polymer are derived from propylene polymerization. In some embodiments, these polymers include homopolymers of propylene.

The propylene-based polymer may include a semi-crystalline polymer. These polymers may be characterized by a crystallinity of at least 25 wt.%, or at least 55 wt.%, or at least 65%, or at least 70 wt.%. Crystallinity can be determined by dividing the heat of fusion of the sample by the heat of fusion of a 100% crystalline polymer, which for polypropylene is designated 209 joules/gram (J/g).

In one or more embodiments, the propylene-based polymer may pass a heat of fusion (H) of at least 52.3J/g, or greater than 100J/g, or greater than 125J/g, or greater than 140J/g_f) To characterize. In some embodiments, the propylene-based polymer may pass H in the range of 52.3J/g and 290J/g_fIncluding any values and subsets therebetween.

In one or more embodiments, useful propylene-based polymers may have a melt Mass Flow Rate (MFR), including any values and subsets therebetween, within the range of 100 decigrams per minute (dg/min) to 0.5dg/min, as determined by ASTM D-1238, 2.16kg at 230 ℃. For example, the propylene-based polymer may have an MFR of less than 100dg/min, or less than 50dg/min, or less than 10dg/min, or less than 5 dg/min. In some embodiments, the propylene-based polymer may have an MFR of at least 0.1dg/min, or 0.2dg/min, or at least 0.5 dg/min. In a preferred embodiment, the propylene-based polymer may have an MFR of from about 0.5dg/min to about 5 dg/min. At one kind orIn various embodiments, useful propylene-based polymers may have a melting temperature (T) of from about 110 ℃ to about 170 ℃, or from about 140 ℃ to about 168 ℃, or from about 160 ℃ to about 165 ℃_m) Including any values and subsets therebetween. They may have a glass transition temperature (T) of from about-10 ℃ to about 10 ℃, or from about-3 ℃ to about 5 ℃, or from about 0 ℃ to about 2 ℃_g) Including any values and subsets therebetween. In one or more embodiments, they can have a crystallization temperature (T) of at least about 75 ℃, or at least about 95 ℃, or at least about 100 ℃, or at least 105 ℃, or in the range of 105 ℃ to 130 ℃_c) Including any values and subsets therebetween.

The propylene-based thermoplastic component can have M in the range of 50,000 g/mole to 1,000,000 g/mole_wIncluding any values and subsets therebetween. M_wMay be greater than 80,000 g/mole, or greater than 100,000 g/mole, or greater than 200,000 g/mole, or greater than 300,000 g/mole. Preferably, M of a propylene-based thermoplastic component_wLess than 500,000 g/mole, or less than 400,000 g/mole, or less than 300,000 g/mole, or less than 250,000 g/mole.

The propylene-based thermoplastic component can have an M in the range of 10,000 g/mole to 600,000 g/mole_nIncluding any values and subsets therebetween. M_nMay be greater than 50,000 g/mole, or greater than 80,000 g/mole, or greater than 100,000 g/mole, or greater than 200,000 g/mole. Preferably, M of a propylene-based thermoplastic component_nLess than 200,000 g/mole, or less than 100,000 g/mole, or less than 80,000 g/mole, or less than 70,000 g/mole.

The propylene-based polymers may be synthesized by catalysis using suitable polymerization techniques known in the art, such as, but not limited to, conventional ziegler-natta type polymerizations, and using single-site organometallic catalysts, including, but not limited to, metallocene catalysts.

As noted above, in some embodiments, the propylene-based polymer comprises a homopolymer of high crystallinity isotactic or syndiotactic polypropylene. Such polypropylene may have a density of about 0.89 to about 0.91g/cc, with highly isotactic polypropylene having a density of about 0.90 to about 0.91g/cc, including any value and subset therebetween. Furthermore, as noted above, high and ultra-high molecular weight polypropylenes with staged melt flow rates can be used. In one or more embodiments, the propylene-based thermoplastic component can be characterized by an MFR (ASTM D-1238, 2.16kg at 230 ℃) that is less than or equal to 10dg/min, or less than or equal to 1.0dg/min, or less than or equal to 0.5 dg/min. In some embodiments, the propylene-based thermoplastic component may be characterized by an MFR (ASTM D-1238, 2.16kg at 230 ℃) in the range of 0.05dg/min to 50dg/min, including any value or subset therebetween.

Examples of suitable propylene-based thermoplastic polymers for use in embodiments of the TPV compositions described herein include EXXONMOBIL^TMPP5341 (available from ExxonMobil Chemical Company); achieve^TMPP6282NE1 (available from ExxonMobil Chemical Company); BRASKEM^TMF008F (available from Braskem, Philadelphia, Pa.); and/or polypropylene resins having broad molecular weight distributions, as described in U.S. patent No. 9,453,093 and U.S. patent No. 9,464,178, which are incorporated herein by reference in their entirety; and/or other polypropylene resins described in U.S. patent publication nos. 2018/0016414 and 2018/0051160 (e.g., PDH025 with a melt flow rate of 2.6g/10min, as shown in the table below), which are incorporated herein by reference in their entirety; WAYMAX^TMMFX6 (a Polypropylene homopolymer with a melt flow rate of 0.8g/10min, available from Japan Polypropylene Corporation); DAPLOY^TMWB140 (available from Borealis AG, Vienna, Austria); and AMPLEO^TM1025MA and AMPLEO^TM1020GA (available from Braskem); and/or other suitable polypropylene; and any combination thereof.

In some embodiments, the thermoplastic component comprises a polyethylene resin alone or in addition to a polypropylene resin. In one or more embodiments, such polyethylene resins comprise at least 90%, or at least 95%, or at least 99%, comprising 100% of polymer units derived from ethylene. In one or more embodiments, the polyethylene resin is a polyethylene homopolymer.

In one or more embodiments, the polyethylene used alone or in conjunction with polypropylene may be passed through M_wFrom about 50 to about 1000 kg/mole, or about 100 to about 500 kg/mole, or about 150 to about 350 kg/mole, including any values and subsets therebetween. Such polyethylenes can be characterized by having a polydispersity index (Mw/Mn) of less than 20, or less than 15, or less than 10, or less than 9. The polyethylene can be characterized by having a polydispersity index (Mw/Mn) of, for example, greater than 2, or greater than 3, or greater than 5, or greater than 10.

In one or more embodiments, the polyethylene used alone or in conjunction with the polypropylene can be characterized by a Melt Flow Index (MFI) (according to ASTM D-1238 at 190 ℃ and 2.16kg load) of 0.1 to 50dg/min, or 0.4 to 12dg/min, or 0.5 to 10dg/min, including any value and subset therebetween.

In one or more embodiments, the polyethylene used alone or in conjunction with the polypropylene can be characterized by an intrinsic viscosity of 0.5 to 10dl/g, or 1.0 to 9.0dl/g, or 1.5 to 8.0dl/g, including any values and subsets therebetween, as determined according to ASTM D1601 and D4020.

In one or more embodiments, the polyethylene used alone or in conjunction with the polypropylene resin may be characterized by a density of greater than 0.8g/cc, or greater than 0.85g/cc, or greater than 0.8g/cc, or greater than 0.93g/cc, or greater than 0.94g/cc, or greater than 0.95g/cc, as measured according to ASTM D4883. In some embodiments, the polyethylene used alone or in conjunction with the polypropylene resin may be characterized by a density of 0.8g/cc to 1.0g/cc as measured by ASTM D4883, including any value or subset therebetween. In one or more embodiments, the polyethylene used alone or in conjunction with the polypropylene can be characterized by an intrinsic viscosity of 0.5 to 10dl/g, or 1.0 to 9.0dl/g, or 1.5 to 8.0dl/g, including any values and subsets therebetween, as determined according to ASTM D1601 and D4020.

Polymers useful as polyethylene, alone or in combination with polypropylene, may be generally referred to as high density polyethylene resins. For example, suitable high density polyethylene resins include those commercially available under the trade designation HDPE HD7960.13 (available from ExxonMobil Chemical Company, Houston, Tex.).

Typically, the thermoplastic component (dispersed phase) comprises from 5 to 90 weight percent, such as from 5 to 70 weight percent, such as from about 5 to 75 weight percent, such as from 7 to 60 weight percent, such as from 7 to 70 weight percent, such as from 10 to 55 weight percent, including any values and subsets therebetween, of the total weight of the thermoplastic vulcanizate composition (including any additives). In some embodiments, the thermoplastic component is included in the TPV composition in an amount of 20 wt% to 70 wt%, including any values and subsets therebetween, of the total weight of the thermoplastic vulcanizate composition. In some embodiments, the thermoplastic component may be present in an amount of from 10phr to 200phr, including any values and subsets therebetween.

Additional additives

The thermoplastic vulcanizate compositions described herein may include any or all of the optional additives described below. The term "additive" and grammatical variations thereof includes any component of the thermoplastic vulcanizates of the present disclosure other than the rubber component and the thermoplastic component. Examples of suitable additives include, but are not limited to, plasticizers (including additive oils), fillers (e.g., particulate fillers), curing agents, compatibilizers, thermoplastic modifiers, lubricants, antioxidants, antiblocking agents, stabilizers, antidegradants, antistatic agents, waxes, blowing agents, pigments, processing aids, adhesives, tackifiers, waxes, discontinuous fibers (e.g., wood cellulose fibers), and any combination thereof.

Various plasticizers may be included in the TPV compositions of the present disclosure used to form the outer protective sheath and/or thermal insulation layer of the catheters described herein. "plasticizer" and grammatical variations thereof refer to a compound, typically a solvent, added to the TPV compositions described herein to create or promote plasticity and flexibility and reduce brittleness. Examples of suitable plasticizers include, but are not limited to, paraffinic oils, aromatic oils, naphthenic oils, synthetic oils, oligomeric plasticizers, and the like, and any combination thereof. The term "plasticizer" is used interchangeably with the term "oil" in this disclosure. Examples of suitable synthetic oils include, but are not limited to, Polyisobutylene (PIB), poly (isobutylene-co-butylene), poly linear alpha olefins, poly branched alpha olefins, hydrogenated poly alpha olefins, and the like, and any combination thereof. Synthetic polyalphaolefins are also suitable plasticizers for use in embodiments of the present disclosure. In some embodiments, the synthetic oil can comprise a synthetic polymer or copolymer having a viscosity of about 20 centipoise (cP) or greater, such as about 100cP or greater, or about 190cP or greater, including any values and subsets therebetween, wherein the viscosity is measured by a Brookfield viscometer according to ASTM D-4402 at 38 ℃. In these or other embodiments, the viscosity of these oils may be about 4,000cP or less, for example about 1,000cP or less, including any values and subsets therebetween.

Oligomeric plasticizers may also be used as plasticizers in embodiments described herein. Examples of suitable oligomeric plasticizers include, but are not limited to, copolymers of isobutylene and butene (butane), copolymers of butadiene along with a supplemental comonomer (isobutylene), high molecular weight copolymers of isobutylene, polyisobutylene in solid or liquid form, and any combination thereof. These oligomeric plasticizers may have a M of less than 1,000_n. Suitable commercially available oligomeric plasticizers include, for example, POLYBUTENE^TM(available from Soltex, Inc. of Houston, Tex.), INDOPOL^TM(available from London BP PLC, UK) and PARAPOL^TM(Houston ExxonMobil Chemical Company, Tex.) of an oligomeric copolymer of isobutylene and butene; and RICON under the trade name^TMThe resin (available from Ricon Resins, inc., grand junction, CO) includes an oligomeric copolymer of butadiene.

In some embodiments, the thermoplastic vulcanizate may include an oil such as a mineral oil, a synthetic oil, or a combination thereof. These oils may also be referred to herein as plasticizers (also known in the art as extenders). Mineral oils may include aromatic oils, naphthenic oils, paraffinic oils, and isoparaffinic oils, synthetic oils, and combinations thereof. In some embodiments, the mineral oil may be treated or untreated. Useful mineral oils are available under the trade name SUNPAR^TM(available from Parsippany, N.J.)-from Sun Chemicals of Troy Hills). Other commercially available oils include PARALUX^TMAnd PARAMOUNT^TMMany oils are derived from petroleum distillates and have specific ASTM designations depending on whether they fall into the categories of paraffinic, naphthenic, or aromatic oils.

Examples of oils include base stocks. Base stocks are classified into five groups based on their saturates content, sulfur level, and viscosity index according to the American Petroleum Institute (API) classification (table a). Lubricating oil (lube) base stocks are typically produced on a large scale from non-renewable petroleum sources. Both group I, II and group III basestocks are derived from crude Oil by large scale processing (e.g., solvent extraction, solvent or catalytic dewaxing, and hydroisomerization, hydrocracking and isodewaxing, isodewaxing and hydrofinishing) [ "New Lubes Plants Use State-of-the-Art hydro dewaxing Technology", Oil & Gas Journal, 1997, 9.1 days; krishna et al, "Next Generation isocyanate and Hydrofinisching technology for Production of High Quality Base Oils", 2002NPRA Lubricants and waxes Meeting, 11 months and 14-15 days 2002; gedeon and Yenni, "Use of" Clean "ParafiniProcess Oils to Improve TPE Properties", published in TPEs 2000, Philadelphia, Pa, on 9 months 27-28 days 1999.

Group III base stocks may also be produced from synthetic hydrocarbon liquids obtained from natural gas, coal, or other fossil resources. Group IV basestocks are Polyalphaolefins (PAOs) and are produced from the oligomerization of alpha olefins, such as 1-decene. Group V base stocks include all base stocks not belonging to groups I-IV, such as cycloparaffins, polyalkylene glycols (PAGs), and esters. The characteristics of groups I-V are provided in Table A.

TABLE A

In some embodiments, the synthetic oil includes oligomers and polymers of butenes including isobutylene, 1-butene, 2-butene, butadiene, and mixtures thereof. In some embodiments, these oligomers may have a number average molecular weight (M) of from about 300g/mol to about 9,000g/mol, and in other embodiments from about 700g/mol to about 1,300g/mol_n) Exemplary synthetic oils include, but are not limited to, polyisobutylene, poly (isobutylene-co-butylene), and mixtures thereof in some embodiments, the synthetic oils may include a poly linear α -olefin, a poly branched α -olefin, a hydrogenated poly α -olefin, and mixtures thereof.

In some embodiments, the synthetic oil comprises a synthetic polymer or copolymer having a viscosity of about 20cP or greater, such as about 100cP or greater, for example about 190cP or greater, wherein the viscosity is measured by a Brookfield viscometer according to ASTM D-4402 at 38 ℃. In these or other embodiments, suitable oils may have a viscosity of about 4,000cP or less, for example about 1,000cP or less.

Useful synthetic oils may be sold under the trade name SOLTEX^TMPolybutene (available from reston Soltex, texas); INDOOL^TMPolybutylene (available from Ineos, a consortium of texas); SPECTRASYN^TMSynthetic white oil (available from ExxonMobil) (raw SHF Fluids); ELEVAST^TMHydrocarbon fluid (available from ExxonMobil); RISELLA^TMWhite oil (available from Shell Global in the Netherlands) produced based on natural gas synthetic oil technology (e.g., RISELLA)^TMX415/420/430)；PRIMOL^TMWhite oil (available from ExxonMobil) (e.g. PRIMOL)^TM352/382/542)；MARCOL^TMWhite oil (available from ExxonMobil) (e.g., MARCOL)^TM82/52); andwhite oil (available from Penreco, Carnes, Pa.) (e.g., as a white oil)

34) Are commercially available. Oils described in U.S. Pat. No. 5,936,028, which is fully incorporated herein by reference, can also be used. Any combination of the foregoing oils may additionally be used without departing from the scope of this disclosure.

Other oils (i.e., plasticizers) may include polymer processing additives such as polymer resins having very high melt flow indices. These polymeric resins include both linear and branched molecules having melt flow rates greater than about 500dg/min, or greater than about 750dg/min, or greater than about 1,000dg/min, or greater than about 1,200dg/min, or greater than about 1,500 dg/min. Typically, these polymer resins have a melt flow rate of less than 10,000 dg/min. Mixtures of various branched or various linear polymer processing additives, as well as mixtures of both linear and branched polymer processing additives, may be used. Preferred linear polymer resins for use as plasticizers in the present disclosure are polypropylene homopolymers or propylene-ethylene copolymers. Preferred branched polymer resins include diene-modified polypropylene polymers. Thermoplastic vulcanizates including similar polymeric resins are disclosed in U.S. Pat. No. 6,451,915, which is incorporated herein by reference in its entirety.

In some embodiments, a plasticizer is included in a TPV composition described herein, including any values and subsets therebetween, for use in forming an outer protective jacket and/or thermal insulation layer in an amount ranging from less than 40 weight percent, such as from 5 weight percent to 40 weight percent, or from 10 weight percent to 40 weight percent, by weight based on the total weight of the thermoplastic vulcanizate composition. In some embodiments, the plasticizer may be present in an amount of from 20phr to 150phr or from 50phr to 150phr, including any values and subsets therebetween.

One or more fillers may be included in the TPV compositions of the present disclosure. "fillers" or "particulate fillers" and grammatical variations thereof may be included in the TPV compositions of the present disclosure to enhance various properties of the TPV compositions, such as strength, toughness, tear resistance, abrasion and flex fatigue, durability, color (i.e., acting as a pigment), and the like, and any combination thereof. The filler may thus be a reinforcing or non-reinforcing filler. Suitable fillers include, but are not limited to, zeolites, carbon black, talc, calcium carbonate, clay, silica, talc, syntactic foams, titanium dioxide, and any combination thereof.

Filler(s) may be included in the TPV compositions used in the conduits described herein, including any values and subsets therebetween, in an amount of 0-30 wt%, or 0-20 wt%, or 0 to 10 wt%, based on the total weight of the thermoplastic vulcanizate composition. I.e., depending at least on the composition of the TPV, the filler may be optional. In some embodiments, the filler may be present in an amount of from 0phr to 100phr, or from 1phr to 100phr, from 0phr to 40phr, or from 1phr to 40phr, or from 5phr to 20phr, including any values and subsets therebetween. In some embodiments, the filler is preferably present in an amount of from 3phr to 10p, or less, inclusive of any values and subsets therebetween, for example for use in thermal insulation layers. When the TPV composition is used as an outer protective layer, a larger amount of filler may be used, for example, in the range of 20phr to 40phr, including any values and subsets therebetween. It is understood that amounts therebetween may be used, for example, when the TPV composition acts as an outer protective layer and a thermal insulation layer. In a preferred embodiment, the filler concentration is from about 3phr to about 10 phr.

In some embodiments, a compatibilizer or compatibilizing agent may be used in the TPV compositions described herein. "compatibilizer" or "compatibilizing agent" and grammatical variations thereof refer to a substance that is included in a TPV composition of the present disclosure to promote interfacial adhesion between the various components of the TPV (e.g., between polymers, fillers, etc.). Examples of suitable compatibilizers include, but are not limited to, maleic anhydride functionalized polypropylene, maleated polypropylene, carboxylated nitrile rubber, styrenic block copolymers, polyolefin based compatibilizers, and the like, and any combination thereof. Exemplary polyolefin-based commercially available compatibilizers include, but are not limited to, INTUNE^TMAnd INFUSE^TMOlefinic block copolymers (available from Dow Chemical Company).

The compatibilizer(s) may be included in the TPV compositions used in the catheters described herein, including any values and subsets therebetween, in an amount of 0.5 to 15 weight percent, or 0.5 to 10 weight percent, or 1 to 5 weight percent of the total weight of the thermoplastic vulcanizate composition. In some preferred embodiments, the compatibilizer may be included in the TPV composition in a range of 3 to 5 weight percent of the total weight of the thermoplastic vulcanizate composition, including any values and subsets therebetween.

In embodiments described herein, a TPV composition for use in a catheter (e.g., a flexible and/or steel catheter) of the present disclosure may include a rubber component (e.g., a crosslinkable rubber component), a thermoplastic component, a curative, and a filler. Optionally, a compatibilizer may be included in the TPV composition. As described above, in some embodiments, the rubber component is crosslinked EPDM, IIR, BIIR, or BIMSM; the thermoplastic component is one or more of polypropylene and/or polyethylene; the plasticizer is a paraffinic oil, polyisobutylene and/or synthetic oil; and the filler is clay. The curing agent may be any of the curing agents described above, such as a metal oxide, a peroxide, a phenolic resin, or a hydrogen containing siloxane.

In most cases, the TPV compositions used in the catheters described herein (e.g., as an outer protective sheath or thermal insulation layer) comprise from about 30 to about 95 weight percent of the rubber component (i.e., the dispersed phase) and from about 5 to about 70 weight percent of the thermoplastic component (i.e., the continuous phase), both based on the total weight of the thermoplastic vulcanizate composition and including any values and subsets therebetween.

The thermal conductivity of the TPV compositions described herein can be less than about 0.20W/mK, for example, in the range of 0.10W/mK to 0.20W/mK, including any values and subsets therebetween. In some embodiments, the TPV composition has a thermal conductivity of less than 0.17W/mK, or less than 0.16W/mK, or less than 0.15W/mK, or less than 0.14W/mK.

In some embodiments, the thermal insulation layer has an abrasion resistance of less than about 3 wt% weight loss based on the total weight of the layer, including 0 wt% weight loss based on the total weight of the layer.

Production of thermoplastic vulcanizates

The TPV compositions described herein can be produced as follows: the method comprises the steps of supplying a rubber component (e.g. a cross-linkable rubber component), a thermoplastic component, a curing agent (e.g. a phenolic resin curing agent) and any further additives to a mixer, such as a screw extruder, and then mixing the components under conditions such that the thermoplastic component melts and the rubber component at least partially cross-links to produce a multiphase product comprising particles of the at least partially cross-linked rubber component dispersed in a matrix comprising the thermoplastic component. Suitable conditions include temperatures of 170-250 deg.C, such as 190-230 deg.C, including any values and subsets therebetween.

The TPV compositions of the present disclosure can be extruded, compression molded, blow molded, injection molded, and/or laminated into various shapes for use in flexible conduits of the present disclosure, whether formed as a single continuous layer or provided in discrete segments. Such shapes may include, but are not limited to, layers (e.g., extruded layers), tapes, strips, castings, moldings, and the like having various thicknesses for providing an outer protective sheath and/or thermal insulation layer for the catheter described herein. In some embodiments, a TPV composition configured for use as at least a portion of a conduit may have a wall thickness (i.e., layer thickness, where multiple layers may be used) in the range of 0.5 millimeters (mm) to 150mm, including any values and subsets therebetween. The particular thickness may depend on one or more factors, including the particular application requirements of the TPV composition as part of the conduit (e.g., whether provided in the outer protective layer or the thermal insulation layer).

Certain embodiments of the TPV compositions described herein are used to form articles made by extrusion and/or coextrusion, blow molding, injection molding, thermoforming, elastic welding (elasto-welding), compression molding, 3D printing, pultrusion, and other suitable manufacturing techniques. Certain embodiments of the TPV compositions of the invention are used to form flexible pipes, tubing, hoses, and flexible structures, such as flexible subsea pipes, flowlines, and flexible subsea umbilicals used in the transportation of fluids in petroleum production. The flexible structure may transport hydrocarbons extracted from offshore deposits and/or may transport water, heating fluids, and/or chemicals injected into the formation to increase the production rate of hydrocarbons. Certain embodiments of the TPV compositions of the present invention are used to form an outer shell of a thermoplastic composite pipe.

Catheter tube

The conduits (i.e., pipes) described herein may comprise various layers, any of which may have a thermal insulation layer or the like bonded thereto, therebetween, a wear resistant and an outer protective jacket. For example, the flexible conduit may include a polymer layer, a metal layer, and a composite layer, with a thermal insulation layer, for example, located below the outer protective sheath. The steel conduit may include an outer protective layer that itself acts as a thermal insulation layer (i.e., the outer protective layer and the thermal insulation layer are the same). In other cases, the steel conduit may be a pipe-in-pipe (e.g., a first pipe nested within a second pipe) conduit and the thermal insulation layer may be located in the annulus between the two pipes.

In some embodiments, the catheter may have the general structure shown in fig. 1, with multiple layers. The inner tube 5 has channels (cans) or holes formed therethrough for the flow of hydrocarbons (e.g., oil and/or gas) and additional components (e.g., water) therewith. The inner tube 5 may be made of a flexible material, including a flat or profiled metallic strip wound helically to provide crush resistance, or alternatively may be composed of steel or other metal. In some cases, the inner tube 5 may be composed of PVDF (e.g., for high temperature and pressure applications), or crosslinked polyethylene and nylon PA11 and/or nylon PA12 (e.g., for mild (mind) temperature and pressure applications), or HDPE (e.g., for low temperature and pressure applications). The reinforcement layer 4 provides additional strength to the catheter and may be made of any metal or metal layer, or alternatively a reinforcement polymer (e.g., carbon nanotube reinforced PVDF). As shown in fig. 1, the thermal insulation layer 3 provides thermal insulation for the conduit and is comprised of the TPV composition described herein (however, conventionally it would be formed of a syntactic polypropylene foam). As shown, the thermal insulation layer 3 is located outside the reinforcement layer 4. Alternatively or additionally, the thermal insulation layer 3 may be located outside the inner tube 5 (e.g., between the inner tube 5 and the reinforcement layer 4) without departing from the scope of the present disclosure. The tensile layer 2 is optional, but if included in the catheter, provides resistance to tensile, torsional and flexural stresses. The outer protective sheath 1 (or outer layer 1) prevents ingress of surrounding fluids (e.g. seawater) and protects against mechanical damage. The outer protective sheath 1 may be comprised of a polymeric material, such as HDPE, or may itself be a thermal insulation layer comprised of the TPV composition of the present disclosure.

Referring now to fig. 2, another catheter that can employ the TPV compositions of the present disclosure is illustrated. As shown, catheter 100 (which is shown as a flexible catheter) includes an inner tube 110 having channels and holes formed therethrough. The tube 110 is made of a flexible material and includes a flat or profiled metallic strip that is helically wound to provide crush resistance. A polymer jacket 120 is at least partially disposed or wrapped around the tube 110 for containing the fluid in the conduit. The sheath 120 is preferably made of an impermeable polymeric material. Layer 130 is at least partially disposed or wrapped around layer 120 and provides resistance to internal pressure, hydrostatic compression, and crushing. Layer 130 may be formed of a helically wound continuous metal strip, preferably of carbon steel, with adjacent windings interlocking to form a flexible layer providing significant hoop and axial strength, such as FLEXLOK^TM(available from Newcastle Wellstream Inc. of Tain, Henan, England). Tensile layer 140 is at least partially disposed or wrapped around layer 130 and includes at least one tensile reinforcing element wrapped to resist hoop stresses, axial components of internal pressure, and axial loads due to the weight of the suspended pipe and external influences. Thermal insulation layer 150 is formed, for example, by extrusion, around tensile layer 140, as is known, from the TPV compositions described herein. An outer protective sheath 160 is at least partially disposed or otherwise formed over the outer tensile layer 150. The jacket 160 may be made from the TPV compositions described herein. In some embodiments, the thermal insulation layer 150 is the same or different composition as the outer protective jacket 160.

Although not shown in the figures, one or more adhesive layers may be provided between any of the layers 110, 120, 130, 140, and 150 of fig. 2 (or layers 1,2, 3, 4, and 5 of fig. 1).

In some embodiments, the present disclosure provides the above descriptionA catheter/conduit (e.g., a flexible catheter) of the type wherein the outer protective sheath or thermal insulation layer comprises a thermoplastic vulcanizate (TPV) composition comprising: (i) a dispersed phase of one or more of butyl rubber and olefinic elastomeric copolymer rubber that has been at least partially cured by a curing agent and (ii) a continuous phase comprising at least one thermoplastic component. The rubber of the dispersed phase preferably comprises polypropylene and the at least one thermoplastic component of the continuous phase comprises isotactic polypropylene. In some embodiments, the at least one thermoplastic component of the continuous phase further comprises high density polyethylene and/or ultra high molecular weight polyethylene. In one or more embodiments, the high density polyethylene comprising the thermoplastic component of the TPV may be polymerized by M_wFrom about 50 to about 1000 kg/mole, or about 100 to about 500 kg/mole, or about 150 to about 350 kg/mole, including any values and subsets therebetween. Such high density polyethylene can be characterized by having a polydispersity index (Mw/Mn) of less than 20, or less than 15, or less than 10, or less than 9. Such high density polyethylene can be characterized by having a polydispersity index (Mw/Mn) higher than 2, or higher than 3, or higher than 5, or higher than 10.

In some embodiments of the present disclosure, the TPV composition comprises a butyl rubber component, such as IIR/BIIR and/or BIMSM. Alternatively, the TPV composition comprises an olefinic elastomeric copolymer, such as EPDM or an ethylene-alpha-olefin-vinyl norbornene rubber (alone or in combination with a butyl rubber). In some embodiments, the rubber component of the dispersed phase is non-halogenated and may be peroxide cured. In some embodiments, the continuous phase comprises polypropylene and optionally also polyamide.

The outer protective jacket and/or thermal insulation layer formed from the TPV compositions described herein may be formed by extrusion onto an underlying layer, such as at least one reinforcing layer, or an inner tube, or a tensile layer. Typically, the outer protective sheath and/or the thermal insulation layer is unfilled, i.e., it does not contain hollow spheres of glass or other brittle material.

Certain embodiments of the present disclosure include (flexible) pipes/catheters comprising a polymeric jacket comprising a TPV composition described herein disposed as an inner, intermediate or outer layer of: 1) unbonded or bonded flexible pipes, tubes and hoses similar to those described in API Spec17J and API Spec 17K, 2) thermoplastic umbilical hoses similar to those described in API17E, or 3) thermoplastic composite pipes similar to those described in DNV RP F119. In other embodiments, the TPV compositions of the present invention are used in composite tapes (e.g., comprising carbon fibers, carbon nanotubes, or glass fibers embedded in a thermoplastic matrix) used in thermoplastic composite tubes similar to those described in DNV RP F119.

To facilitate a better understanding of embodiments of the present invention, the following examples of preferred or representative embodiments are given. The following examples should not be construed in any way to limit or define the scope of the disclosure.