Extruder Systems and Processes

Abstract

The present disclosure relates to an extruder system and process thereof. In at least one embodiment, a method for forming a dynamically crosslinked thermoplastic elastomer (TPV) composition includes introducing a thermoplastic polymer into an extruder through a feed throat. The elastomeric polymer is introduced into a melt feeder to form an elastomeric polymer melt comprising the elastomeric polymer. The melt feeder is coupled to the extruder. The elastomeric polymer melt from the melt feeder is introduced into the extruder. The thermoplastic polymer and the elastomeric polymer melt are fed separately into the extruder. The thermoplastic polymer and the elastomeric polymer melt in the extruder are mixed using multiple intermesh screws having multiple mixing zones.

Description

[Technical field]

[0001] The present disclosure relates to extruder systems and processes. [Background technology]

[0002]

[0002] Thermoplastic vulcanizate (TPV) or dynamic vulanized alloy (DVA) products are chemically crosslinked rubber encapsulated in a thermoplastic phase. TPVs are typically produced by a combination of distributive and dispersive mixing in the presence of a phenolic resin curing catalyst system to obtain a uniform dispersion of small particle size EPDM rubber in a polypropylene phase.

[0003]

[0003] Automotive equipment manufacturers and suppliers are increasingly using TPV compositions in automotive weather seals in place of EPDM or other thermoset compounds. The increased use of TPV compositions is due in part to advantages in processability and recyclability. The lip is a highly elastic and resilient portion of the weather seal structure. For example, the lip should instantly shrink and return to its original position when deflected against glass, for example at temperatures up to about 90°C.

[0004]

[0004] In addition to elasticity, TPV compositions should have an excellent balance of other mechanical properties such as hardness and tensile strength. Additionally, extrusion applications such as glass run channels require excellent surface finish of the TPV composition free of defects such as edge tears, surface spots, and optical defects. Poor elastic properties are in part related to the high yield stress of the TPV composition in the molten state, resulting in poor flow / melt stagnation.

[0005]

[0005] Therefore, there is a need to develop TPV compositions that have a good balance of elastic and mechanical property combinations, as well as good flow and extrusion processability.

[0006]

[0006] References cited in the Information Disclosure Statement (37 CFR 1.97(h)) include U.S. Patent No. 7,655,728; U.S. Patent No. 10,077,344; U.S. Patent No. 8,158,721; and U.S. Patent No. 9,296 / 885. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 7,655,728 [Patent Document 2] U.S. Patent No. 10,077,344 [Patent Document 3] U.S. Patent No. 8,158,721 [Patent Document 4] U.S. Patent No. 9,296 / 885 Summary of the Invention [Problem to be solved by the invention]

[0008] The present disclosure relates to an extruder system and process. [Means for solving the problem]

[0009] In at least one embodiment, a method of forming a dynamically crosslinked thermoplastic elastomer (TPV) composition includes the steps of introducing a thermoplastic polymer into an extruder through a feed throat. An elastomeric polymer is introduced into a melt feeder to form an elastomeric polymer melt comprising the elastomeric polymer. The melt feeder is coupled to the extruder. The elastomeric polymer melt from the melt feeder is introduced into the extruder. The thermoplastic polymer and the elastomeric polymer melt are fed separately into the extruder. The thermoplastic polymer and the elastomeric polymer melt in the extruder are mixed using multiple intermesh screws having multiple mixing zones.

[0010] In at least one embodiment, the extruder system includes a first end, a second end, and a plurality of ports disposed along the extruder. At the first end of the extruder, a feed throat is coupled to a first port of the plurality of ports. A melt feeder is coupled to a second port of the plurality of ports downstream of the first port. A hardener source is coupled to a third port of the plurality of ports, the third port being disposed downstream or upstream of the second port. A melt pump is coupled to the second end of the extruder.

[0011] In at least one embodiment, a method includes forming a dynamically crosslinked thermoplastic elastomer (TPV) composition. The method includes the steps of introducing a thermoplastic polymer into an extruder through a feed throat at a first location. The elastomeric polymer is introduced into a melt feeder to form an elastomeric polymer melt comprising the elastomeric polymer, the melt feeder being coupled to the extruder. The elastomeric polymer melt is introduced from the melt feeder into the extruder at a second location downstream of the first location. The thermoplastic polymer and the elastomeric polymer melt are mixed in the extruder using a plurality of intermeshing screws. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present disclosure relates to an extruder system and a process for using the extruder system to form a TPV product.

[0013]

[0012] TPV products are chemically crosslinked rubber encapsulated in a thermoplastic phase. TPVs are produced using a combination of distributive and dispersive mixing in the presence of a resin curing catalyst system.

[0014] It has been found that TPV compositions with enhanced elasticity, flow, and surface properties can be obtained by processing the material with the extruder system of the present disclosure and using the methods provided herein. The improved surface properties include improved extrusion surface roughness (ESR) and surface spots. Without being bound by theory, it is believed that the improved surface properties may be due to the reaction kinetics produced by the extruder system and methods described herein, which alter the kinetics of phase inversion of a well-mixed product. The systems and methods provided herein provide enhanced uniform dispersion of very small vulcanized rubber particles, e.g., vulcanized rubber particles having a diameter of about 5 nm or less, e.g., less than about 3 nm.

[0015] For purposes of this disclosure, when a polymer is said to contain an olefin, the olefins present in the polymer are the respective polymerized forms of olefins. Similarly, use of the term polymer is meant to encompass homopolymers and copolymers, with copolymers including any polymer having two or more chemically distinct monomers.

[0016] For purposes of this disclosure, the term "polypropylene," as used herein, means a polymer containing propylene as a monomer, which may be a homopolypropylene or a copolymer of propylene and an α-olefin comonomer.

[0017] For purposes of this disclosure, the term "polyethylene," as used herein, means a polymer containing ethylene as a monomer, which may be a homopolyethylene or a copolymer of ethylene and an α-olefin comonomer.

[0018]

[0017] A "composition," as used herein, can include the components of the composition and / or the reaction products of one or more of the components.

[0019] Method for preparing TPV composition In some embodiments, a method for forming a dynamically crosslinked thermoplastic elastomer (TPV) composition includes introducing a thermoplastic polymer into an extruder through a feed throat. The elastomeric polymer is introduced into a melt feeder coupled to the extruder to form an elastomeric polymer melt. The elastomeric polymer melt from the melt feeder is introduced into the extruder. The thermoplastic polymer and the elastomeric polymer melt are fed separately into the extruder and mixed in the extruder in multiple mixing zones of the screw / extruder using multiple intermesh screws. In some embodiments, the thermoplastic polymer is introduced into the extruder through a feed throat at a first location. The elastomeric polymer melt from the melt feeder is introduced into the extruder at a second location downstream of the first location. The thermoplastic polymer and the elastomeric polymer melt in the extruder are mixed together using multiple intermesh screws. The thermoplastic polymer can be a polypropylene homopolymer, a polyethylene homopolymer, a propylene ethylene copolymer, or a combination thereof.

[0020]

[0019] The multiple mixing sections include at least three mixing sections. At least one of the mixing sections has a greater mixing intensity than another mixing section among the at least three mixing sections. In some embodiments, the second mixing section has a greater mixing intensity than each of a first mixing zone upstream of the second mixing zone and a third mixing zone downstream of the second mixing zone among the at least three mixing zones. In some embodiments, the mixing intensity of a mixing zone located in the first one-half to three-quarters of the length of the extruder is greater than the mixing intensity of a mixing zone located along the other length of the extruder. The thermoplastic polymer and elastomeric polymer melt are mixed in the extruder at a total effective mixing intensity of about 690 to about 830. The thermoplastic polymer and elastomeric polymer melt are mixed at a total effective mixing intensity of about 7,000 s. -1 ~about 12,000 seconds -1 During mixing, the average extrusion temperature is about 160°C to about 320°C.

[0021] In these or other embodiments, the amount of thermoplastic polymer in the thermoplastic phase may be from about 5 parts to about 350 parts by weight of rubber, such as from about 7 parts to about 100 parts, or from about 20 parts to about 150 parts, such as from about 25 parts to about 150 parts, such as from about 50 parts to about 150 parts, such as from about 60 parts to about 100 parts (parts per hundred parts by weight of rubber, or "phr"). The thermoplastic phase is introduced into the extruder separately from the rubber, for example through a feed port located near the first end of the extruder.

[0022]

[0021] The thermoplastic polymer is introduced at a first location in the extruder and the elastomeric polymer melt is introduced at a second location, the second location being downstream of the first location, the first and second locations being respectively disposed within the first 1 / 16 to 1 / 4 of the length of the extruder.

[0023] In some embodiments, fillers (e.g., calcium carbonate, clay, silica, talc, titanium dioxide, nucleating agents, mica, wood flour, etc., and blends thereof, as well as inorganic and nanoscale organic fillers) may be added to the TPV composition in an amount of about 100 phr or less. In some embodiments, the fillers are introduced into the extruder in an amount of about 10 phr or less, such as about 1 phr to about 4 phr, e.g., about 1.5 phr, or about 2.0 phr, along with a reaction moderator (e.g., a cure moderator) in a powder blend. In some embodiments, the cure moderator is a phenolic resin.

[0024]

[0023] Small amounts of fillers, such as clays (e.g., about 100 phr or less), are used as powder blends to dilute or feed small amounts of set moderators. The resulting products with small amounts of fillers have a smooth surface with no or substantially no edge tears, no or substantially no die lines, and / or no or substantially no visible surface gels.

[0025]

[0024] The powder blend is introduced upstream of the second position of the extruder. The powder blend can be introduced into a feed throat located at the first position of the extruder. In some embodiments, the powder blend is introduced together with the thermoplastic polymer. In a typical process where the thermoplastic layer and the rubber are introduced together without a melt feeder, a significant amount of filler is required to assist the process. It has been found that the use of a melt feeder to heat and treat the rubber before introducing it into the extruder eliminates the need for a large amount of filler and enhances product quality.

[0026]

[0025] The cure accelerator, for example, a cure accelerator masterbatch, is introduced into the feed throat in an amount of less than 3 phr, for example, from about 0.5 phr to about 2.0 phr. The cure accelerator is stannous chloride, zinc oxide, or a combination thereof.

[0027]

[0026] The carbon black material is introduced into the extruder at a location upstream of the second location. The carbon black is introduced into the extruder separately from the rubber. In some embodiments, the carbon black material is a carbon black masterbatch, which is introduced into the extruder at the feed throat. The carbon black masterbatch is introduced at about 5 phr to about 30 phr, for example, about 10 phr to about 20 phr. The amount of carbon black masterbatch depends on the desired product grade.

[0028] In some embodiments, the TPV composition includes a curing agent, such as a phenolic resin curing agent. The phenolic resin curing agent is introduced into the extruder downstream of the melt feeder. The curing agent is introduced via a liquid pump coupled to the extruder at a third location downstream of the second location (e.g., at the location of the melt feeder). The third location is located in the first one-third to two-thirds of the length of the extruder. The curing agent is introduced in an amount of about 3 phr to about 10 phr.

[0029] The process oil is introduced into the extruder at one or more locations, such as upstream of the hardener, downstream of the hardener, downstream of the melt feeder, downstream of the feed throat, or combinations thereof. In some embodiments, the process oil is a paraffinic oil. Process oil may also refer to a plasticizer or extender, such as mineral oil, synthetic oil, ester plasticizer, or combinations thereof. Mineral oils may include aromatic oils, naphthenic oils, paraffinic oils, isoparaffinic oils, synthetic oils, and combinations thereof. In some embodiments, the mineral oil may be treated or untreated. Useful mineral oils may be available under the trade name SUNPAR™ (Sun Chemicals). Other oils are available under the trade names PARALUX™ (Chevron), and PARAMOUNT™ (Chevron), e.g., Paramount™ 6001R (Chevron Phillips). Other oils that may be used include hydrocarbon oils and plasticizers, e.g., organic esters and synthetic plasticizers. Many additive oils are derived from petroleum fractions and have specific ASTM designations depending on whether they fall into the paraffinic, naphthenic, or aromatic oil classes. Other types of additive oils include alpha-olefin synthetic oils, e.g., liquid polybutylene. Additive oils other than petroleum-based oils can also be used, examples of which include oils derived from coal tar and pine tar, as well as synthetic oils, e.g., polyolefin materials. Examples of oils include base stocks.

[0030]

[0029] Process oil is introduced into the extrusion in an amount of from about 25 phr to about 41 phr, divided among one or more positions in the extruder.

[0031]

[0030] An extrudate is formed from the thermoplastic polymer and elastomeric polymer melt from the extruder to a twin screw melt pump to form a composition. The composition is removed from the twin screw melt pump and can be used as a feedstock to form an end product such as an automotive product, e.g., a weather seal. The composition can be molded and conditioned into a test sample according to the specific specifications for the test. The composition (e.g., TPV composition) has an extrusion surface roughness (ESR) of about 25 μin to about 50 μin, as measured according to the ESR procedure described in Chemical Surface Treatments of Natural Rubber And EPDM Thermoplastic Elastomers: Effects on Friction and Adhesion, RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 67, No. 4 (1994), which is incorporated herein by reference.

[0032] Weatherseals can be formed from the TPV compositions using a weatherseal extrusion line, for example, a 2.5 inch 30:1 extruder with a single or dual screw design and mixer. The TPV compositions formed using the extruder system and process described herein have a head pressure drop of about 40% or less compared to a control composition made by simultaneously introducing a thermoplastic polymer and an elastomeric polymer into an extruder. "Head pressure drop," as used herein, refers to the increase in die pressure during a profile extrusion test. A lower pressure increase indicates better processability. Motor amperage was about 10% to about 30% compared to the control composition. Without being bound by theory, it is believed that the reduced head pressure drop and amperage is due to the reduced amount of filler used in the TPV compositions of the present disclosure. It is therefore believed that the TPV compositions described herein can be more easily processed into a final product compared to conventional TPV compositions.

[0033] The TPV composition has about 23 or less surface spots using visual observation of three strips. The strips are prepared according to the ESR procedure. Each of the strips, having a strip surface of about 150 linear centimeters, is inspected for visible spots. The visible spots protruding from the surface are counted. The total number of spots on each strip is counted and is within about 0.80 mm. 2 (0.001 in 2 ) or greater are counted.

[0034] Extruder System In at least one embodiment, the extruder system includes a first end, a second end, and a plurality of ports disposed along the extruder. The feed throat is coupled to a first port of the plurality of ports at the first end of the extruder. The melt feeder is coupled to a second port of the plurality of ports downstream of the first port. The hardener source is coupled to a third port of the plurality of ports, the third port being disposed downstream or upstream of the second port. The melt pump is coupled to the second end of the extruder. The process oil pump is coupled to a fourth port of the plurality of ports upstream or downstream of the third port.

[0035]

[0034] The melt feeder provides the extruder with a polymer (e.g., elastomeric polymer) melt, reducing or eliminating the need to granulate the elastomeric polymer (e.g., rubber) before introducing it to the extruder. The process for granulating the rubber includes introducing a partitioning filler to prevent reagglomeration of the granulated rubber in the final product. The use of fillers is reduced with the process described herein. In particular, small amounts of fillers such as clay may be used to mix with the reaction moderator or to feed a small amount of the reaction moderator as a powder blend. The resulting product with a small amount of filler is smooth, has no or substantially no edge tears, no or substantially no die lines, and / or has no or substantially no visible gels on the surface.

[0036] It has been found that a melt pump, such as a twin screw melt pump, located at the exit of the extruder eliminates the occurrence of a side stream of lubricant backflow into the main stream being extruded by the extruder.

[0037] The screws used in the extruder are intermeshing screws and co-rotating screws.

[0038]

[0037] The extruder of the present disclosure may have any suitable number of ports, number of screws, number of barrels, barrel length, solid barrel and combination barrel configurations depending on the process parameters used. One or more screws may be blocking screws. Blocking screws can be designed to prevent crossover of material from one part of the extruder to another part of the extruder. Blocking screws may be fixed position or solid rotating.

[0039] Transitioning extrudate from one flow zone to the next in an extruder is defined as exiting the conveying zone and entering the mixing zone, or exiting the mixing zone and entering the conveying zone.

[0040]

[0039] The elements of the screw can be classified as one of conveying elements, kneaders, backflow elements, flow splitters, or restrictive conveying elements. In some embodiments, the screw of the present disclosure includes one or more conveying elements, one or more kneaders, one or more backflow elements, one or more flow splitters, one or more restrictive conveying elements, or combinations thereof, in any suitable configuration. The conveying elements are screws with flutes with various pitches, designed to move the extrudate forward in the mixing barrel. Kneaders tend to restrict the flow of the extrudate, which provides thorough shear, particle size reduction, and heat generation. The backflow elements are equipped with flutes that reverse the flow of the extrudate and act as restrictive or blocking elements. The restrictive conveying elements may be single flight elements with wide crests or may have slotted flights, kneading the extrudate as it is conveyed forward. The restrictive conveying elements may have low pitch flights or high pitch flights with slots.

[0041]

[0040] Screw elements are commercially described in their design by letter and number designations. Number and letter designations and screw elements are available from Century Extruders, Traverse City, Michigan.

[0042]

[0041] S and SK refer to conveying elements that perform some mixing, but are primarily used to push the material in the extruder from the end of the melt feeder to the end of the extruder. SK elements are conveying elements that have more free volume than normal conveying elements and are used as transition elements between flow zones. SG refers to elements that convey the extruded material while providing substantial mixing.

[0043]

[0042] KB refers to the kneading element. The kneader has no significant bias in the direction of moving the extrusion material forward and tends to fill the material from the upstream in the extruder. The kneader may include any number of plates, and the plates may have one or more points. For example, a kneading plate with two points has a general parallelogram shape with two points corresponding to the maximum diameter of the plate, and a plate with three points has three similar maximum diameter points and three corresponding flat areas with diameters close to the diameter of the screw shaft. If a backflow conveyor is used with the kneader, it ensures filling of the flow zone around the kneader, and the increased pressure and shear caused by the filling tends to dramatically increase the temperature of the extrusion material.

[0044]

[0043] The numbers in the screw element symbol refer to the flute pitch, the length of the element, and the number of plates in the element. Additional letters refer to its orientation, left (L) or right (R), and its type. In the description, the letter "N" means that the element is "neutral" and provides no conveying action in either direction.

[0045] For example, S060R030 refers to a conveying element (S) with a flute pitch of 060 mm to the right (R) and a length of 30 mm. Similarly, KBS405R030 refers to a kneader (KBS) with 5 plates with a 45° separation between the tips of adjacent plates and a conveying bias to the right and a length of 30 mm. S040RL040 Igel and KBS905N030 are flow splitting elements that cut the extrusion flow into two or more streams and direct the split streams back to the left (L) and right (R). These flow splitting elements cause a crossover between the internal and external extrudate streams. S030L015 refers to a backflow conveying element with a pitch of 30 mm to the left (L) and a length of 15 mm. The L designation describes that the flute pitch direction tends to push the extrusion material back to the feed throat, sometimes called backflow.

[0046]

[0045] Backflow elements, kneaders and other non-conveying or low-conveying elements cause pressure to build up in that particular flow zone until the pressure of the feed material and the pressure caused by the upstream conveying elements overcomes the back pressure and forces the extrusion material into the respective flow zone.

[0047]

[0046] Backflow elements, when used, are placed at the end of a flow or mixing zone. Because a backflow element creates a barrier, it is considered to define the end of a flow zone. Similarly, a restrictive conveying element creates high pressure in its flow zone, so the end of such an element where the pressure is released to the forward conveying element is considered to be the end of the flow zone.

[0048]

[0047] The function of each flow zone can be defined by its shear rate and the number of shears that take place in the flow zone. Kneaders and flow splitters, in addition to the mixing they provide, are used, for example, to melt the extrudate and increase its temperature, and are designed to generate a lot of shear. Conveying elements provide some mixing, but are primarily designed to move the extrudate in a given direction and do not generate as much shear as kneaders. Most of the other mixing elements fall between the kneaders and the conveying elements in terms of their mixing capacity and their shear capacity.

[0049]

[0048] As exemplified in U.S. Pat. No. 4,594,390, shear rate is defined as C x RPM / tip clearance, where "tip clearance" is the distance between the tip of the screw and the wall of the extrusion chamber (e.g., mixing barrel) and C is the circumference of the element. In other words, shear rate is the tip revolutions divided by the tip clearance. Thus, the shear number is "shear rate" x "length of a particular flow zone", and shear rate is directly related to the mixing aggressiveness of a particular screw profile. In the process of the present disclosure, a 400 sec -1 or greater shear rates can be effectively used.

[0050]

[0049] Substantial shear occurs between the tip of the screw and the bottom of the grooves of the adjacent intermesh screw, and while previous calculations do not fully account for this mixing process, for purposes of this disclosure, the mixing capacity of a particular screw profile can be described in terms of the "mesh" of the screw, and the "intermeshes" of multiple intermesh screws. "Mesh," as used herein, refers to the mixing capacity of a particular screw element or profile, and "intermesh" refers to the mixing capacity of multiple intermesh screws.

[0051]

[0050] The amount of shear generated by a particular screw element depends on the profile of that element, and the amount of shear generated between the screw tip and the mixing barrel is an inherent characteristic of the element profile, and calculation of the screw mesh and intermesh is a more satisfactory method of determining the processing capacity of a screw profile than the methods described in the prior art.

[0052]

[0051] When the screw is rotating at a particular RPM during processing, the number of intermeshes / sec, or intermeshes per second, can be calculated as a measure of the amount of mixing that occurs in the extrudate. The amount of mixing that results in the processing of a particular extrudate further depends on the feed rate of the materials, the RPM of the extrusion screw, the viscosity ratio and temperature of the materials, their surface wetting characteristics, the surface tension of the particles, and their flow characteristics.

[0053]

[0052] The FCA is the cm that exists between the screw elements, the barrel surface, and the core. 2 The FCA is the free cross-sectional area in units. The material feed rate into the extruder is specified based on the FCA. For example, in a 30 mm ring extruder, the FCA provided by the manufacturer is 26.2 cm 2 At 400 RPM and 200 Kg / hr, material feed rate = (200 Kg / hr) / (26.2 cm 2 ) = 7.63 kg / (time x cm 2 ), and at 100 RPM and 50 Kg / hr, material feed rate = (50 Kg / hr) / (26.2 cm 2 ) = 1.91 kg / (time x cm 2 ).

[0054]

[0053] In practice, the speed, screw speed, barrel temperature, and other process conditions are often optimized to obtain the target product properties during scale-up. It may be important to maintain similar residence times, melting temperatures, curing, and mixing profiles along the screw axis in different size extruders so that the quality is similar during scale-up. In some embodiments, extrusion is carried out at an extrusion temperature (e.g., barrel internal temperature) of about 26°C (80°F) to about 371°C (700°F), such as about 65°C (150°F) to about 204°C (400°F), such as about 82°C (180°F) to about 148°C (300°F).

[0055]

[0054] The speed for scale-up at the same screw speed can be calculated by multiplying the material feed rate of the known extruder by the desired or target FCA of the extruder and the target diameter ratio of the known extruder. This is further illustrated with an example where the speed of a 50 mm ring extruder is calculated from data from a 30 mm size tool at 400 RPM. Speed 50mm (kg / hour) = (Material feed rate (kg / (hour × cm 2 ))) 30mm ×FCA 50mm ×(50mm / 30mm)=7.63kg / (time×cm 2 )×74.1cm 2 x 1.67 = 944 kg / hour.

[0056]

[0055] The important parameters that define the mixing imparted by the extruder during the process are related as follows: The degree of mixing is a function of the No. of Tips factor, Pitch factor, Length or L / D factor, Restriction factor, Free Cross-sectional Area (FCA), RPM, and Rate.

[0057] Regardless of the material used, the meshes per second in a particular flow zone can be found by multiplying the restriction factor by the length factor, multiplying by the pitch factor, multiplying by the number of tips factor, and multiplying by the revolutions per second. The number of intermeshes / second can be found by multiplying the resulting number by the number of screws used in the extrusion.

[0058] The screws of the present disclosure may have a mesh of 450 to 1020, such as a mesh of 500 to 900, such as a mesh of 700 to 800. The screws may have a mesh of about 10 to 23 per L / D, such as a mesh of about 11 to about 20, such as a mesh of about 11 to about 16 per L / D, where the mesh per L / D is calculated by dividing the mesh of a given screw design by the L / D.

[0059] For the purposes of this disclosure, a flow zone or mixing zone can be further defined as a set of one or more mixing elements or a set of one or more conveying elements. The end points of each zone are defined by the transition from a conveying element to a mixing element or vice versa. For example, a KB60 / 3 / 30 followed by a K60 / 3 / 30 can be one zone. However, a KB60 / 3 / 30 followed by a 45 / 45 or any other mixing element would imply a separation between two different zones. Thus, theoretically, a 100 L / D screw can have 200 mixing zones if all 0.5 L / D mixing and conveying elements are used. Those skilled in the art will recognize that larger diameter machines can use screw elements with less than 0.5 L / D.

[0060]

[0059] For purposes of quantifying the mixing characteristics of a particular screw profile, a restriction factor was assigned to each of the elements used in the screw profile based on the mixing factor determined by the number of plates, shear and contact area (e.g., restrictive conveying elements have a shorter pitch and higher residence time, the pressure in the zone increases), and their function (e.g., backflow), as well as the tip radial clearance between the barrel or adjacent screw elements.

[0061] Table 1 shows the constraint factors assigned to particular screw elements.

[0062] [Table 1]

[0063]

[0061] The SFL, LHKB, and LHCE elements are considered to have a higher restriction factor (55, 6, and 50, respectively) when placed after a mixing element, and a less restrictive effect (20, 3, and 15, respectively) when placed after a conveying element. A higher restriction factor is assigned when more than one left hand element is placed next to another left hand element.

[0064] To describe the mixing value of a particular screw profile in absolute terms, it is appropriate to describe the screw in terms of its mesh, i.e., the mixing capacity of the screw independent of the rotational speed, L / D, and number of screws used. By dividing the number of meshes of a screw design by its L / D, one can obtain a calculated number of meshes per L / D for that screw design.

[0065] In some embodiments, a screw having a maximum L / D of 100 with a maximum of 23 meshes per L / D and a maximum of 170 mixing zones can be used. In some embodiments, as few as 3 mixing zones and 10 meshes per L / D can be used. Thus, the process can be carried out using a screw having a L / D of 15-100, with 3-170 mixing zones and 3-17 meshes (per L / D). In some embodiments, the screw of the present disclosure has a L / D of about 40 to about 50.

[0066]

[0064] The mesh calculations for the individual elements are shown in the mesh table (Table 3). In the table, the elements are listed by type, pitch factor, length factor (denoted L / D), number of flight tips in the element, confinement factor, and effective element strength. The confinement factor column indicates the mixing ability of the element in the mesh.

[0067] In the calculations, pitch factor = screw diameter / pitch, e.g. 30mm / 60mm = 0.5. This applies to SG, SK and S elements, but not to KBS, Igel, LH elements or kneading blocks. The length factor applies to all elements.

[0068]

[0066] The number of tips for an element in the mesh table is the number of flights times the number of elements or discs, for elements or discs with a single flight this is 1 x 1 = 1. For double flighted elements the number of tips is 2 x 5 = 10 for a kneading block with double flights of 5 discs, 2 x 5 = 10 for 5 segmented Igels with double flights and 2 x 6 = 12 for 6 segmented SG elements. For a kneading block with triple flights with 5 discs the number of tips is 3 x 5 = 15. By following these examples this calculation can be used for conveying or mixing elements with more than three flights.

[0069] [Table 2]

[0070]

[0067] The sum of the effective element intensities of each element in the screw profile is the effective element intensity shown in the last column of the above mesh table (Table 2). The total effective mixing intensity of the screw. In some embodiments, the screw of the present disclosure rotates at a speed of about 100 rpm (revolutions per minute) to about 500 rpm, such as about 200 rpm to about 400 rpm, such as about 275 rpm to about 375 rpm. In some embodiments, the screw of the present disclosure operates at a total effective mixing intensity of about 600 to about 900, such as about 700 to about 800, such as about 750 to about 780.

[0071]

[0068] The total mixing intensity is the sum of the mixing intensities of each element in the screw design and the effective element strength. The total mixing intensity can be determined using Equation 1:

[0072] Total mixed strength = element pitch factor x element L / D x number of element flight tips x element limit factor (Equation 1) Finally, the dynamic mixing intensity of a screw design can be a key evaluation of the degree of mixing power. For example, since there are a total of two rotating screws in an extrusion process, the dynamic mixing intensity is the degree of mixing power obtained and the second -1 Multiply the process RPM in units of and multiply by a factor of 2. Dynamic mixing intensity can be determined using Equation 2.

[0073] Dynamic mixing intensity = number of meshes x screw speed x number of screws (Equation 2) For example, for a non-limiting example screw in a twin screw extruder mixing TPV at 350 rpm, the dynamic mixing intensity is 8,903 sec-1 In some embodiments, the screw of the present disclosure may be rotated for about 6,000 seconds. -1 ~about 10,500 seconds -1 It operates at a dynamic mixing intensity of, for example, about 7,000 seconds -1 ~about 9,500 seconds -1 , for example, about 8,000 seconds -1 ~about 9,000 seconds -1 It operates at a dynamic mixing intensity of .

[0074] The length of the screw can be considered to have approximately equal mixing sections, for example, four equal quartiles. Quartile 3 of the screw profile is shown in Table 3 to be the dominant region of mixing intensity regardless of extruder rpm.

[0075] The first quartile of the screw is the quartile located near the first end of the screw, e.g., the quartile located near the feed throat of the extruder. In some embodiments, the first quartile of the screw of the present disclosure is about 700 sec. -1 ~Approx. 1,800 seconds -1 It operates at a dynamic mixing intensity of, for example, about 800 seconds -1 ~Approx. 1,600 seconds -1 , or about 1,000 seconds -1 ~Approx. 1,800 seconds -1 In some embodiments, the second quartile of screws of the present disclosure operates at a dynamic mixing intensity of about 900 s -1 ~about 2,100 seconds -1 It operates at a dynamic mixing intensity of, for example, about 1,000 seconds -1 ~Approx. 1,900 seconds -1 , or about 1,200 seconds -1 ~about 2,100 seconds -1 In some embodiments, the third quartile of the screws of the present disclosure operates at a dynamic mixing intensity of about 2,900 s -1 ~about 5,800 seconds -1 It operates at a dynamic mixing intensity of, for example, about 3,000 seconds -1 ~about 5,000 seconds -1 , or about 3,100 seconds -1~about 5,600 seconds -1 In some embodiments, the fourth quartile of the screws of the present disclosure operates at a dynamic mixing intensity of about 1,000 s. -1 ~about 2,000 seconds -1 For example, it operates at a dynamic mixing intensity of about 1,100 seconds. -1 ~Approx. 1,900 seconds -1 , for example, about 1,100 seconds -1 ~Approx. 1,500 seconds -1 , alternatively about 1,600 seconds -1 ~Approx. 1,900 seconds -1 Each of the first, second, third and fourth sections (eg, quartiles) are in sequence with one another from the upstream end to the downstream end of the extruder.

[0076] In some embodiments, the screws of the present disclosure operate at a total effective mixing intensity of about 500 to about 1,100, such as about 600 to about 900, such as about 700 to about 800. In some embodiments, the first quartile of the screws of the present disclosure operate at a total effective mixing intensity of about 80 to about 160, such as about 100 to about 140, such as about 110 to about 130. In some embodiments, the second quartile of the screws of the present disclosure operate at a total effective mixing intensity of about 100 to about 200, such as about 110 to about 190, such as about 130 to about 170. In some embodiments, the third quartile group of screws of the present disclosure operates at a total effective mixing intensity of about 280 to about 460, e.g., about 290 to about 450, e.g., about 280 to about 440. In some embodiments, the fourth quartile group of screws of the present disclosure operates at a total effective mixing intensity of about 80 to about 200, e.g., about 90 to about 170, e.g., about 100 to about 160. In some embodiments, the fifth quartile group of screws of the present disclosure operates at a total effective mixing intensity of about 110 to about 200, e.g., about 130 to about 170, e.g., about 145 to about 155. In some embodiments, in the third quartile group, a substantial amount of hardening occurs.

[0077] [Table 3]

[0078] The mixing elements such as the ZME, TME, SME, and elongational flow elements have meshes of 20, 15, 10, and 35, respectively. The calculations shown can be applied to elements of any diameter, L / D, number of flights or lobes, or number of disks. One skilled in the art would be able to use each calculation to determine the number of intermeshes to be used in a particular extrusion. For example, if the screw has a mesh of 396 and six screws are used at 360 RPM, the number of intermeshes / sec would be 396 x 6 / sec x 6 = 14,256.

[0079] In some embodiments, a screw profile can be used that has about 15 to about 40 mixing zones, for example about 60% to 71% of which about 25 to about 35 mixing zones are conveying elements, about 20% to 40% are mixing elements (kneaders with pitch), and about 2% to 6% are restrictive conveying elements, in which case the screw has a mixing capacity of 543 to 850 mesh. The L / D ratio of the screw profile can be L / D36 to L / D60.

[0080]

[0076] In some embodiments, the screws of the present disclosure have a total mesh of 500-850.

[0081]

[0077] The residence time of the extrudate in the extruder of the process of the present disclosure can be empirically determined by adding a dye to the feed throat of the extruder after the start of extrusion from the die and measuring the time for a color change to appear at the extrusion die. In some embodiments, the residence time can be from 15 to 180 seconds depending on the material being processed.

[0082]

[0078] In some embodiments, process oil is added at one or more locations along the extruder to control the temperature and consistency of the composition as it is processed, as well as to control the properties of the final extrudate product.

[0083] In some embodiments, the specific energy of the ring extruder is about 0.17 to 0.28 Kw / Kg.

[0084]

[0080] In some embodiments, the extruder can be operated at an output capacity of from about 10 kilograms per hour (kg / hr) to about 6,000 kg / hr, such as from about 10 kg / hr to about 300 kg / hr, alternatively from about 300 kg / hr to about 1,500 kg / hr, alternatively from about 1,500 kg / hr to about 3,000 kg / hr, and alternatively from about 3,000 kg / hr to about 6,000 kg / hr.

[0085] Melting Feeder The melt feeder of the present disclosure may be any suitable melt feeder, such as a melt feeder commercially available from Bonnot, Inc., Akron, Ohio. An elastomeric polymer may be introduced into the melt feeder and heated to form an elastomeric polymer melt. The melt feeder is coupled to an extruder to introduce the elastomeric polymer melt to the extruder. The polymer melt may include a softened feed, a molten feed, or a combination thereof.

[0086]

[0082] The melt feeder may include a motor coupled to a first end of a gear box. The gear box is coupled at a second end to a first end of a hopper. The hopper includes a plurality of grinders having a plurality of teeth configured to grind the solid feed into small particles. The grinders may be actuated (e.g., rotated) by the motor and the gear box. The hopper is coupled at a second end to a first end of an auger barrel. A plurality of heating jackets are disposed around the auger barrel, each heating jacket corresponding to a heating zone and providing controlled heating of the small particles from the hopper.

[0087] The feed fed to the hopper may be of any suitable size. For example, the feed may have an average size of about 3 inches or less, such as about 2 inches or less. The small particles formed from the hopper may have a size of about 0.5 inches or less, such as about 0.25 inches or less. The small particles are directed into the interior space of the auger barrel. A screw is rotatably disposed within the auger barrel. In use, rotation of the screw draws the feed / particles / melt from the hopper and moves the feed / particles / melt through the barrel during heat treatment of the feed / particles / melt.

[0088]

[0084] The front end of the screw is coupled (e.g., connected) to a gear box. The gear box is configured to rotate the screw during use. In some embodiments, the screw has a width of about 1 inch to about 10 inches, such as about 2 inches to about 6 inches, such as about 3 inches to about 4 inches. The screw includes a plurality of flights. The spacing between the flights of the plurality of flights can vary, for example, the spacing between the flights is greater near the front end of the screw and then continuously decreases or decreases at some point along the front of the screw.

[0089]

[0085] The heating jacket is configured to heat the feed / particles / melt as they move inside the auger barrel by the rotation of the screw. The heating jacket may have any suitable size or configuration, or there may be any suitable number of heating jackets. The heating jacket may be heated by flowing and / or circulating a fluid (e.g., heated oil, steam, etc.) through the heating jacket, and / or may be an electric heater. Typically, the heating jacket is configured to heat the feed material (e.g., polymer) to a temperature of about 60°C to about 180°C, such as about 80°C to about 120°C. Heating the feed material at the start or front of the melt feeder evaporates moisture, if present in the feed.

[0090]

[0086] The melt feeder can be coupled to (e.g., connected to) an extruder at the end of the feeder to provide the polymer melt to the extruder to initiate functionalization of the polymer, e.g., as described above. In some embodiments, the polymer melt is provided to the extruder at a rate of about 40 kg / hr to about 4,000 kg / hr, e.g., about 1,000 kg / hr to about 3,000 kg / hr.

[0091] In some embodiments, the melt feeder is coupled to the extruder (used to functionalize the polymer) in a first portion of the extruder (e.g., the first one-eighth to one-half of the length, e.g., one-quarter of the length). For example, the melt feeder may be coupled to the extruder at a location that corresponds to the flow zone of a screw used in the extruder to functionalize the polymer. The terms "first" and "remaining" are used with respect to the direction in which the extrudate flows through the extruder.

[0092] Melt Pump

[0088] The melt pump of the present disclosure, such as a melt pump, may be any suitable melt pump, for example a twin screw melt pump, such as a melt pump commercially available from Henschel GmbH, Germany. The melt pump is connected at a first end to a second end of the extruder and at a second end to a first end of the extrusion die.

[0093] The melt pump may be a multi-screw extruder (e.g., a twin screw extruder) with a horizontal screw configuration, where the feed is fed / removed in an up / down relative configuration. The melt pump may have a cylindrical housing that operates at temperature using a heating cartridge and water cooling. The melt pump may have one or more screws with a diameter of about 60 millimeters (mm) to about 200 mm, for example about 100 mm to about 140 mm. In use, the screws rotate at a constant speed of about 15 minutes. -1 ~ approx. 160 minutes -1 For example, the rotation may be performed at a speed of about 53 minutes. -1 ~ approx. 150 minutes -1 , alternatively about 31 minutes -1 ~ approx. 94 minutes -1 , alternatively about 23 minutes -1 ~ approx. 69 minutes -1 , alternatively about 16 minutes -1 ~About 47 minutes -1The screw may be rotated at a speed of from about 4 kilowatts (kW) to about 140 kW, such as from about 4 kW to about 12 kW, alternatively from 11 kW to about 36 kW, alternatively from 23 kW to about 70 kW, alternatively from 45 kW to about 140 kW. The melt pump may be operated at an output torque of from about 700 Newton meters (Nm) to about 28,300 Nm, such as from about 3,600 Nm to about 9,800 Nm. The melt pump can operate at an output capacity of about 10 kilograms per hour (kg / hr) to about 6,000 kg / hr, such as about 10 kg / hr to about 300 kg / hr, alternatively about 300 kg / hr to about 1,500 kg / hr, alternatively about 1,500 kg / hr to about 3,000 kg / hr, alternatively about 3,000 kg / hr to about 6,000 kg / hr. The melt pump can operate at a pressure of about 100 bar to about 500 bar, such as 200 bar to about 350 bar.

[0094] The melt pump can be designed to rotate the twin screw at a rotational speed of about 30 rpm to about 300 rpm, for example about 50 rpm to about 150 rpm, depending on the type of extrudate. The selected rotational speed can be selected so that the melt is conveyed with significantly reduced or no pulsation.

[0095]

[0091] Gears may be arranged between the compressor and, advantageously, an electric drive, so that the twin screws can be driven synchronously. Due to this synchronization, a geometrically accurate interlocking of the flights with respect to one another is possible. As a result, one screw of the twin screws is advantageously not moved by a mechanically forced connection, as is the case with geared pumps according to known examples, but is driven directly, thus avoiding high friction with the known disadvantages of high energy consumption and the accompanying temperature increase. This also makes it possible to operate the twin screws so that each screw rotates in the opposite direction. The synchronization from the gears is further advantageous in that the drive force can also be introduced directly into both twin screws in order to achieve a better force distribution.

[0096]

[0092] As an example, the flights of both twin screws may intermesh with each other in such a way that the flight gap remaining in the narrowest position forms a gap seal. This gap seal prevents backflow of the extrudate, increases the forced feed and also acts as an overpressure counterbalance. The forced feed causes high pressure build-up, while the pressure counterbalance prevents damage to the extrudate, more specifically if the gap seal is adapted to the medium to be processed. The same advantage may also be applied to the gap of the housing.

[0097]

[0093] Another advantage is that the twin screw can be driven with relatively low power, which results in a smaller drive motor and less energy consumption.

[0098]

[0094] Furthermore, a number of chambers are formed between the housing and the twin screws or their flights in which the extrudate is placed. The chambers can be pseudo-closed according to gap seals and / or gaps in the housing so that the desired pressure can be built up, but in instances with localized excess pressure, pressure compensation occurs.

[0099]

[0095] Moreover, the chamber extends along the pitch of the flights. The beginning and end of the chamber are therefore located at the intersection of the two twin screws (for example in the plane defined by the axes of the two twin screws), which is advantageous in that the extrudate occupies a defined location and is not mixed with another medium. At the same time, this allows an efficient pressure build-up on the perforated disk.

[0100]

[0096] A gap in the housing can be formed between the flight and the casing, and a gap is formed between the flight and its adjacent counter rotating twin screw, both of which form a gap seal such that the medium is substantially retained in the respective chamber without significant backflow of the medium through the gap (e.g., gap seal) into the adjacent rear chamber. This is advantageous in that a seal is achieved between the chambers, thereby allowing high pressures in each chamber and pressures of about 400 to about 600 bar at the perforated disc, and temperatures of about 100°C to about 300°C.

[0101]

[0097] The housing gap and / or gap may have a width of about 0.05 mm to about 2 mm. The width of the gap, and therefore the size of the gap seal, will ultimately depend on the media to be processed and its additives.

[0102]

[0098] The twin screw is designed so that the ratio of the outer diameter to the core diameter is approximately 2. Depending on the type of melt (extrudate), a ratio of Da to Di can also be selected having a range of about 1.6 to about 2.4, which results in a large delivery volume being achieved using a relatively thin and therefore cost-effective melt pump. With a length / diameter ratio of the counter-rotating twin screws of about 2 to about 5, for example about 3.5, the vessel can achieve a pressure of about 250 bar to about 600 bar and a temperature of about 100°C to about 350°C on the perforated disk. This is advantageous in that the melt pump can be manufactured at low cost and can be utilized in a small space.

[0103]

[0099] A relatively rapid build-up of pressure is achieved by the cooperation of two precisely intermeshing twin screws and correspondingly designed flights. High pressures are achieved and the retention period in the vessel is relatively short, reducing the possibility of thermal and mechanical damage to the extrudate.

[0104] TPV composition In some embodiments, the TPV composition may include the elastomeric polymer in an amount of about 5 wt% to about 95 wt%, such as about 10 wt% to about 90 wt%, such as about 20 wt% to about 85 wt%, such as about 45 wt% to about 80 wt%, such as about 60 wt% to about 75 wt%, based on the combined weight of the elastomeric polymer and the thermoplastic polyolefin. The elastomeric polymer is also referred to herein as "rubber", which is a dynamically-vulcanized rubber, such as an ethylene-based copolymer, such as an ethylene propylene diene terpolymer.

[0105]

[0101] In at least one embodiment, the amount of rubber in the TPV composition may be from about 5 wt% to about 95 wt%, such as from about 10 wt% to about 90 wt%, such as from about 20 wt% to about 85 wt%, such as from about 45 wt% to about 80 wt%, such as from about 60 wt% to about 75 wt%, based on the combined weight of the rubber phase and the thermoplastic phase, and the thermoplastic phase comprises from about 1.5 wt% to about 45 wt%, such as from about 10 wt% to about 40 wt%, such as from about 12 wt% to about 30 wt%, of a thermoplastic polymer or thermoplastic polyolefin, such as a propylene-based polymer, an ethylene-based polymer, a butene-1-based polymer, or a combination thereof, based on the combined weight of the rubber phase and the thermoplastic phase.

[0106]

[0102] The process for providing uniform dispersion of small particle size elastomeric polymers, such as EPDM rubber, in thermoplastic polymers, such as polypropylene, results in a locked-in morphology that provides physical properties similar to thermoset rubber. Specifically, the process provides excellent tensile strength and elasticity. Improved processability and extrusion properties of TPVs are key to end-use applications, since TPVs are the primary components of extruded parts such as automotive weather stripping. Improving the process further enhances factors such as processability and surface appearance.

[0107] Rubber Phase

[0103] Rubbers that can be employed to form the rubber phase include polymers that can be cured or crosslinked by moisture curing with phenolic resins or hydrosilylation curing agents (e.g., silicone hydrides), peroxides with coagents, silane grafting, or azides. The rubber phase is crosslinked after the rubber is introduced into the extruder. The rubber phase may be in the form of finely divided particles of vulcanized or cured rubber that can be dispersed within a continuous thermoplastic phase, which can also be referred to as a matrix. Reference to rubber can include mixtures of more than one rubber. Non-limiting examples of rubbers include terpolymers of olefinic elastomers, and mixtures thereof. In some embodiments, terpolymers of olefinic elastomers include ethylene-based elastomers, such as ethylene-based copolymer rubbers and ethylene-propylene-non-conjugated diene rubbers.

[0108] Ethylene-Based Copolymers

[0104] The term ethylene-based copolymer refers to a rubber-like terpolymer polymerized from ethylene, at least one other α-olefin monomer, and at least one diene monomer (e.g., ethylene-propylene-diene terpolymer or EPDM terpolymer). The α-olefin monomers can include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or combinations thereof. In at least one embodiment, the α-olefin monomers can include propylene, 1-hexene, 1-octene, or combinations thereof. The diene monomer may include 5-ethylidene-2-norbornene (ENB); 5-vinyl-2-norbornene (VNB); 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; or combinations thereof. Polymers prepared from ethylene, α-olefin monomers, and diene monomers may also be referred to as terpolymers, or, if multiple α-olefin monomers or dienes are used, tetrapolymers. An example of an ethylene-based copolymer is ethylene-propylene copolymer rubber (or ethylene-propylene copolymer).

[0109]

[0105] In some embodiments, the ethylene-based copolymer may have an ethylene-derived content of about 10 wt% to about 99.9 wt% (e.g., about 10 wt% to about 90 wt%, e.g., about 12 wt% to about 90 wt%, e.g., about 15 wt% to about 90 wt%, e.g., about 20 wt% to about 80 wt%, e.g., about 40 wt% to about 70 wt%, e.g., about 50 wt% to about 70 wt%, e.g., about 55 wt% to about 65 wt%, e.g., about 60 wt% to about 65 wt%) based on the total weight of the ethylene propylene rubber. In some embodiments, the ethylene-derived content is about 40 wt% to about 85 wt%, e.g., about 40 wt% to about 85 wt%, based on the total weight of the ethylene propylene rubber.

[0110]

[0106] In some embodiments, the ethylene-based copolymer may have a diene-derived content of about 0.1 wt% to about 15 wt%, such as about 0.1 wt% to about 5 wt%, such as about 0.2 wt% to about 10 wt%, such as about 2 wt% to about 8 wt%, or about 4 wt% to about 12 wt%, such as about 4 wt% to about 9 wt%, based on the total weight of the ethylene propylene rubber. In some embodiments, the diene-derived content may be about 3 wt% to about 15 wt%, based on the total weight of the ethylene propylene rubber.

[0111] In some embodiments, when the diene monomer comprises 5-ethylidene-2-norbornene (ENB) and / or 5-vinyl-2-norbornene (VNB), the ethylene-based copolymer may comprise at least about 0.1 wt % (e.g., at least about 1 wt %, e.g., at least about 3 wt %, e.g., at least about 4 wt %, e.g., at least about 5 wt %) of the diene monomer based on the total weight of the ethylene propylene rubber. In these and other embodiments, when the diene comprises ENB or VNB, the ethylene-based copolymer may comprise from about 1 wt % to about 15 wt % (e.g., from about 3 wt % to about 15 wt %, e.g., from about 4 wt % to about 12 wt %, e.g., from about 5 wt % to about 12 wt %, e.g., from about 7 wt % to about 11 wt %) of the diene monomer based on the total weight of the ethylene propylene rubber.

[0112] In some embodiments, the ethylene-based copolymer may have oil in an amount ranging from about 0 phr (parts per hundred parts by weight of rubber) to about 200 phr, such as from about 0 phr to about 100 phr, for example, between 75 phr and 100 phr.

[0113] In some embodiments, the ethylene-based copolymer has an α-olefin-derived content (e.g., C2 to C 40 For example, C3~C 20 For example, C3~C 10The balance may be ethylene propylene rubbers containing olefins such as propylene.

[0114] In some embodiments, the ethylene-based copolymers may have a weight average molecular weight (Mw) of about 100,000 g / mol or higher (e.g., about 200,000 g / mol or higher, e.g., about 400,000 g / mol or higher, e.g., about 600,000 g / mol or higher). In these or other embodiments, the Mw may be about 1,200,000 g / mol or less (e.g., about 1,000,000 g / mol or less, e.g., about 900,000 g / mol or less, e.g., about 800,000 g / mol or less, e.g., about 400,000 g / mol to about 700,000 g / mol). In these or other embodiments, the Mw may be about 400,000 g / mol and about 3,000,000 g / mol (e.g., about 400,000 g / mol to about 2,000,000, e.g., about 400,000 g / mol to about 1,500,000 g / mol, e.g., about 400,000 g / mol to about 1,000,000 g / mol or about 600,000 g / mol to about 1,200,000 g / mol, e.g., about 600,000 g / mol to about 1,000,000 g / mol).

[0115] In some embodiments, the ethylene-based copolymer may have a number average molecular weight (Mn) of about 20,000 g / mol or higher (e.g., about 60,000 g / mol or higher, e.g., about 100,000 g / mol or higher, e.g., about 150,000 g / mol or higher). In these or other embodiments, Mn may be less than about 500,000 g / mol (e.g., about 400,000 g / mol or less, e.g., about 300,000 g / mol or less, e.g., about 250,000 g / mol or less).

[0116]

[0112] In some embodiments, the ethylene-based copolymer may have a Z-average molecular weight (Mz) of about 10,000 g / mol to about 7,000,000 g / mol (e.g., about 50,000 g / mol to about 3,000,000 g / mol, e.g., about 100,000 g / mol to about 2,000,000 g / mol, e.g., about 200,000 g / mol to about 1,500,000 g / mol, e.g., about 200,000 g / mol to about 1,00,000 g / mol, e.g., about 200,000 g / mol to about 500,000 g / mol).

[0117]

[0113] In some embodiments, the ethylene-based copolymer may have a polydispersity index (Mw / Mn; PDI) of from about 1 to about 15 (e.g., from about 1 to about 10, e.g., from about 1 to about 5, e.g., from about 1 to about 4, e.g., from about 2 to about 4 or from about 1 to about 3, e.g., from about 1.8 to about 3, or from about 1 to about 2, or from about 1 to about 2.5).

[0118] In some embodiments, the ethylene-based copolymer has a dry Mooney viscosity (ML at 125° C.) according to ASTM D1646 of about 10 MU to about 500 MU, or about 50 MU to about 450 MU. (1+4) In these or other embodiments, the Mooney viscosity is about 50 or greater, such as about 250 MU or greater, such as about 350 MU or greater.

[0119] In some embodiments, the ethylene-based copolymer has a g' of 0.7 or greater. vis (e.g. about 0.75 or greater, such as about 0.8 or greater, 0.85 or greater, such as 0.9 or greater, such as 0.95 or greater, such as about 0.96, about 0.97, about 0.98, about 0.99, or about 1).

[0120] In some embodiments, the ethylene propylene rubber has a glass transition temperature (T) of about -20°C or less (e.g., about -30°C or less, e.g., about -50°C or less), as measured by differential scanning calorimetry (DSC) according to ASTM E1356. g In some embodiments, T g is about -20°C to about -60°C.

[0121]

[0117] In some embodiments, the ethylene-based copolymer may have a large amplitude oscillatory shear (LAOS) branching index of less than about 10, such as less than about 5, such as from about -1 to about 5. In at least one embodiment, the ethylene-based copolymer may have a LAOS branching index of less than about 3.

[0122]

[0118] In some embodiments, the ethylene-based copolymer may have an LCB Index (at 125°C) of about 2.5 or lower, such as about 2.0 or lower.

[0123]

[0119] In at least one embodiment, the ethylene-based copolymer may have a Δδ of about 30 degrees to 80 degrees from small amplitude oscillatory shear (SAOS), e.g., about 32° or greater, e.g., about 35° or greater. Δδ is the difference in phase angle (δ) at frequencies of 0.1 and 128 rad / sec, e.g., derived from a frequency sweep at 125°C, i.e., in this case Δδ(125°C)=δ(0.1 rad / sec)-δ(128 rad / sec).

[0124]

[0120] Ethylene-based copolymers can be produced or synthesized by using various techniques. For example, these terpolymers can be synthesized by employing various catalyst systems, such as Ziegler-Natta systems containing vanadium catalysts, and employing solution, slurry or gas phase polymerization techniques or combinations thereof, conducted in various phases, such as solution, slurry or gas phase. Exemplary catalysts include single-site catalysts, including constrained geometry catalysts, including Group IV-VI metallocenes. In some embodiments, EPDM can be produced via conventional Ziegler-Natta catalysts using slurry processes, particularly those containing vanadium compounds, as disclosed in U.S. Pat. No. 5,783,645, as well as via metallocene catalysts, as also disclosed in U.S. Pat. No. 5,756,416. Other catalyst systems, such as Brookhart catalyst systems, can also be employed. Optionally, such EPDM can be prepared using the above catalyst systems in a solution process.

[0125] In some embodiments, the rubber may be highly cured. In some embodiments, the rubber is advantageously partially or fully (fully) cured. The degree of cure can be measured by determining the amount of rubber extractable from the TPV composition by using cyclohexane or boiling xylene as an extractant. This method is disclosed in U.S. Pat. No. 4,311,628, which is incorporated herein by reference for purposes of U.S. patent practice. In some embodiments, the rubber has a degree of cure that is about 5.9 wt.% or less, such as about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, extractable by cyclohexane at 23° C., as described in U.S. Pat. Nos. 5,100,947 and 5,157,081, which are incorporated herein by reference for purposes of U.S. patent practice. In these or other embodiments, the rubber is cured to the extent that greater than about 94 wt.%, such as greater than about 95 wt.%, such as greater than about 96 wt.%, such as greater than about 97 wt.%, based on the weight of the rubber, is insoluble in cyclohexane at 23° C. Alternatively, in some embodiments, the rubber has a crosslink density of at least 4×10 -5 Moles / ml of rubber, e.g. at least 7 x 10 -5 Moles / ml of rubber, e.g. at least 10 x 10 -5 and has a degree of cure such that it is in the range of moles per milliliter of rubber. See also Ellul et al., "Crosslink Densities and Phase Morphologies in Dynamically Vulcanized TPEs," RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 68, pp. 573-584 (1995).

[0126]

[0122] Despite the fact that the rubber may be partially or fully cured, the TPV compositions of this disclosure can be processed and reworked by conventional plastic processing techniques such as extrusion, injection molding, blow molding, and / or compression molding to form articles. The rubber in these thermoplastic elastomers may be in the form of finely divided, well-dispersed particles of vulcanized or cured rubber in a continuous thermoplastic phase. In some embodiments, a co-continuous morphology or phase inversion may be achieved. In embodiments where the cured rubber is in the form of finely divided, well-dispersed particles in the thermoplastic medium, the rubber particles may have an average diameter of about 50 μm or less (e.g., about 30 μm or less, e.g., about 10 μm or less, e.g., about 5 μm or less, e.g., about 1 μm or less). In some embodiments, at least about 50%, e.g., about 60%, e.g., about 75%, of the particles have an average diameter of about 5 μm or less, e.g., about 2 μm or less, e.g., about 1 μm or less.

[0127]

[0123] Some terpolymer elastomers are commercially available under the trade names Vistalon™ (ExxonMobil Chemical Co.; Houston, TX), Keltan™ (Arlanxeo Performance Elastomers; Orange, TX), Nordel™ IP (Dow), NORDEL MG™ (Dow), Royalene™ (Lion Elastomers), and Suprene™ (SK Global Chemical). Specific examples include Vistalon™ 3666, EXP-Vistalon (manufactured according to WO2017127184A1), Keltan™ 5469Q, Keltan™ 4969Q, Keltan™ 5469C, Keltan™ 4869C, Royalene™ 694, Royalene™ 677, Suprene™ 512F, Nordel™ 6555, Keltan 5467C, and Nordel™ 4555OE.

[0128]

[0124] In some embodiments, the ethylene propylene rubber may be obtained in an oil extended form with from about 50 phr to about 200 phr of process oil, for example from about 75 phr to about 120 phr of process oil, based on 100 phr of ethylene propylene rubber.

[0129] thermoplastic layer In some embodiments, the thermoplastic layer of the TPV composition comprises a polymer capable of flowing at a temperature above its melting temperature. In some embodiments, the major component of the thermoplastic layer comprises at least one thermoplastic polyolefin, such as polypropylene (e.g., homopolymer, random copolymer, or impact copolymer, or a combination thereof), an ethylene-based polymer (e.g., polyethylene), or a butene-based polymer (e.g., polybutene). In some embodiments, the thermoplastic layer may also comprise, as a minor component, at least one thermoplastic polyolefin, such as an ethylene-based polymer (e.g., polyethylene), a propylene-based polymer (e.g., polypropylene), or a butene-based polymer (e.g., polybutene).

[0130] 1. Propylene-based polymers

[0126] Propylene-based polymers include solids, generally high molecular weight plastic resins that contain units derived primarily from the polymerization of propylene. In some embodiments, at least 75%, in other embodiments at least 90%, in other embodiments at least 95%, and in other embodiments at least 97% of the units of the propylene-based polymer are derived from the polymerization of propylene. In some embodiments, these polymers include homopolymers of propylene. Homopolymer polypropylene may contain linear chains and / or chains with long chain branches.

[0131] In some embodiments, the propylene-based polymer also contains units resulting from the polymerization of ethylene and / or α-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 mixtures thereof. Specifically, the propylene-based polymer also contains units resulting from the polymerization of ethylene and / or the higher α-olefins described above, or C 10 ~C 20These include reactor, impact, and random copolymers with olefins.

[0132] In some embodiments, the propylene-based polymer comprises semi-crystalline polymer. In some embodiments, these polymers can be characterized by at least 25wt% or more crystallinity (e.g., about 55wt% or more, e.g., about 65wt% or more, e.g., about 70wt% or more crystallinity). Crystallinity can be determined by dividing the heat of fusion (Hf) of a sample by the heat of fusion of 100% crystalline polymer, which is assumed to be 209 Joules / gram for polypropylene.

[0133] In some embodiments, the propylene-based polymer may have an Hf of about 52.3 J / g or greater (eg, an Hf of about 100 J / g or greater, such as about 125 J / g or greater, such as about 140 J / g or greater).

[0134]

[0130] In some embodiments, the propylene-based polymer may have a weight average molecular weight (Mw) of about 50,000 g / mol to about 2,000,000 g / mol (e.g., about 100,000 g / mol to about 1,000,000 g / mol, e.g., about 100,000 g / mol to about 600,000 g / mol or about 400,000 g / mol to about 800,000 g / mol), as measured by GPC using polystyrene standards.

[0135]

[0131] In some embodiments, the propylene-based polymer may have a number average molecular weight (Mn) of about 25,000 g / mol to about 1,000,000 g / mol (e.g., about 50,000 g / mol to about 300,000 g / mol) as measured by GPC using polystyrene standards.

[0136] In some embodiments, the propylene-based polymer has a g' of about 1 or less (eg, 0.9 or less, such as 0.8 or less, such as 0.6 or less, such as 0.5 or less). vis In some embodiments, the polypropylene may have a g' greater than about 0.90, such as greater than about 0.97. vis In some embodiments, the polypropylene may have a g' of about 0.7 to about 0.88. vis has.

[0137] In some embodiments, the propylene-based polymer may have a melt mass flow rate (MFR) (ASTM D1238, 2.16 kg weight at 230° C.) of about 0.1 g / 10 min or more (e.g., about 0.2 g / 10 min or more, e.g., about 0.2 g / 10 min or more). Alternatively, the MFR may be from about 0.1 g / 10 min to about 50 g / 10 min, e.g., from about 0.5 g / 10 min to about 5 g / 10 min, e.g., from about 0.5 g / 10 min to about 3 g / 10 min.

[0138] In some embodiments, the propylene-based polymer has a melting temperature (T) of about 110° C. to about 170° C. (e.g., about 140° C. to about 168° C., e.g., about 160° C. to about 165° C.). m ) may be included.

[0139] In some embodiments, the propylene-based polymer has a glass transition temperature (T) of about −50° C. to about 10° C. (e.g., about −30° C. to about 5° C., e.g., about −20° C. to about 2° C.). g ) may be included.

[0140] In some embodiments, the propylene-based polymer has a crystallization temperature (T) of about 75° C. or higher (e.g., about 95° C. or higher, e.g., about 100° C. or higher, e.g., about 105° C. or higher (e.g., about 105° C. to about 130° C.). c ).

[0141]

[0137] In some embodiments, the propylene-based polymer may include a homopolymer of highly crystalline isotactic or syndiotactic polypropylene. The polypropylene may have a density of about 0.89 to about 0.91 g / ml, and the mostly isotactic polypropylene has a density of about 0.90 to about 0.91 g / ml. Also, high and ultra-high molecular weight polypropylenes with slight melt flow rates may be employed. In some embodiments, the polypropylene resin may be characterized by an MFR (ASTM D-1238; 2.16 kg at 230°C) of about 10 dg / min or less (e.g., about 1.0 dg / min or less, e.g., about 0.5 dg / min or less).

[0142] In some embodiments, the polypropylene may include homopolymer, random copolymer, or impact copolymer polypropylene or combinations thereof. In some embodiments, the polypropylene is a high melt strength (HMS), long chain branched (LCB) homopolymer polypropylene.

[0143]

[0139] The propylene-based polymers can be synthesized by using any suitable polymerization technique known in the art, such as conventional Ziegler-Natta type polymerization or catalysis employing single-site organometallic catalysts, such as metallocene catalysts.

[0144]

[0140] Examples of polypropylenes useful in the TPV compositions described herein include ExxonMobil™ PP5341 (available from ExxonMobil); Achieve™ PP6282NE1 (available from ExxonMobil) and / or broad molecular weight distribution polypropylene resins as described in US 9,453,093 and US 9,464,178; and other polypropylene resins described in US 20180016414 and US 20180051160 (e.g., EXP-PP as shown in the table below); Waymax™ MFX6 (available from Japan Polypropylene Corp.); Borealis Daploy™ WB140 (available from Borealis AG); and Braskem Ampleo 1025MA and Braskem Ampleo 1020GA (Braskem Ampleo). (Available from Ampleo). Table 5 shows the characteristics of selected propylene-based polymers. g' vis can be measured using GPC-4D. Techniques for determining molecular properties are described below.

[0145] [Table 4]

[0146] 2. Ethylene-based polymers

[0141] Ethylene-based polymers include solid, generally high molecular weight plastic resins that contain units derived primarily from the polymerization of ethylene. In some embodiments, at least 90%, in other embodiments at least 95%, and in other embodiments at least 99% of the units of the ethylene-based polymers may be derived from the polymerization of ethylene. In certain embodiments, these polymers include homopolymers of ethylene.

[0147]

[0142] In some embodiments, the ethylene-based polymer may also contain units resulting from the polymerization of α-olefin comonomers, such as propylene, 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof.

[0148]

[0143] In some embodiments, the ethylene-based polymer may have a melt index (MI) (ASTM D1238, 2.16 kg at 190°C) of about 0.1 dg / min to about 1,000 dg / min (e.g., about 1.0 dg / min to about 200 dg / min, e.g., about 7.0 dg / min to about 20.0 dg / min).

[0149] In some embodiments, the ethylene-based polymer has a melting temperature (T) of about 140° C. to about 90° C. (e.g., about 135° C. to about 125° C., e.g., about 130° C. to about 120° C.), as measured by differential scanning calorimetry (DSC) at 10° C. / min. m ) may be included.

[0150] Ethylene-based polymers can be synthesized by using suitable polymerization techniques known in the art, such as conventional Ziegler-Natta type polymerization or catalysis employing single-site organometallic catalysts, such as metallocene catalysts. Some ethylene-based polymers are commercially available. For example, polyethylene is commercially available under the trade name ExxonMobil™ polyethylene (ExxonMobil). Ethylene-based copolymers are commercially available under the trade name ExxonMobil™ polyethylene (ExxonMobil), including metallocene-produced linear low density polyethylenes such as Exceed™, Enable™, and Exceed™ XP.

[0151] In some embodiments, the ethylene-based polymer can include low density polyethylene, linear low density polyethylene, or high density polyethylene. In some embodiments, the ethylene-based polymer can be a high melt strength (HMS) long chain branched (LCB) homopolymer polyethylene.

[0152]

[0147] Other ethylene-based polymers that can be used include Hostalen (LBI), Paxxon (ExxonMobil), and Escorene (ExxonMobil).

[0153] 3.1-Butene-based polymers

[0148] Butene-1 based polymers include solids, generally high molecular weight isotactic butene-1 resins containing units derived primarily from the polymerization of 1-butene.

[0154] In some embodiments, the 1-butene-based polymer may include isotactic poly(butene-1) homopolymer. In some embodiments, the 1-butene-based polymer may also include units resulting from the polymerization of α-olefin comonomers, such as ethylene, propylene, 1-butene, 1-hexane, 1-octene, 4-methyl-1-pentene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-hexene, and mixtures of two or more thereof.

[0155]

[0150] In some embodiments, the 1-butene-based polymer includes one or more of the following characteristics.

[0156] In some embodiments, the 1-butene-based polymers may have at least 90 wt% or more (e.g., about 95 wt% or more, e.g., about 98 wt% or more, e.g., about 99 wt% or more) units of 1-butene-based polymers derived from the polymerization of 1-butene. In some embodiments, these polymers may include homopolymers of 1-butene.

[0157] In some embodiments, the 1-butene-based polymer may have a melt index (MI) (ASTM D1238, 2.16 kg at 190° C.) that may be from about 0.1 dg / min to about 800 dg / min (e.g., from about 0.3 dg / min to about 200 dg / min, e.g., from about 0.3 dg / min to about 4.0 dg / min). In these or other embodiments, the MI may be about 500 dg / min or less (e.g., about 100 dg / min or less, e.g., about 10 dg / min or less, e.g., about 5 dg / min or less).

[0158] In some embodiments, the 1-butene-based polymer has a melting temperature (T), as measured by DSC at 10° C. / min, that can be from about 130° C. to about 110° C. (e.g., from about 125° C. to about 115° C., e.g., from about 125° C. to about 120° C.). m ) may be included.

[0159] In some embodiments, the 1-butene-based polymer may have a density, as determined according to ASTM D 792, which may be from about 0.897 g / ml to about 0.920 g / ml, such as from about 0.910 g / ml to about 0.920 g / ml. In these or other embodiments, the density may be about 0.910 g / ml or greater, such as 0.915 g / ml or greater, such as about 0.917 g / ml or greater.

[0160]

[0155] 1-butene-based polymers can be synthesized by using suitable polymerization techniques known in the art, such as conventional Ziegler-Natta type polymerization or catalysis employing single-site organometallic catalysts, such as metallocene catalysts. Some 1-butene-based polymers are commercially available. For example, isotactic poly(1-butene) is commercially available under the trade name polybutene resin or PB (Basell).

[0161] Hardener

[0156] In some embodiments, the rubber is cured or crosslinked by dynamic vulcanization. The term dynamic vulcanization refers to the vulcanization or curing process of the rubber contained in the blend with the thermoplastic resin, where the rubber is crosslinked or vulcanized under high shear conditions at a temperature above the melting point of the thermoplastic. The rubber can be cured by employing various curative systems, including a curative. Exemplary curatives include phenolic resin curing systems, peroxide curing systems, silicon-based curing systems (e.g., hydrosilylation and silane grafting, followed by moisture curing), sulfur-based curing systems, or combinations thereof.

[0162]

[0157] The dynamic vulcanization may be carried out in the presence of the thermoplastic polyolefin, the thermoplastic polyolefin may be added after the dynamic vulcanization (e.g., after addition), or both (e.g., some polyolefin may be added before the dynamic vulcanization and some polyolefin may be added after the dynamic vulcanization).

[0163] Useful phenolic curing systems are disclosed in US Pat. Nos. 2,972,600, 3,287,440, 5,952,425 and 6,437,030.

[0164]

[0159] In some embodiments, the phenolic resin curing agent includes resole resins, which can be prepared by condensation of alkyl-substituted or unsubstituted phenols with aldehydes, such as formaldehyde, in alkaline medium, or by condensation of difunctional phenol dialcohols. The alkyl substituent of the alkyl-substituted phenols can have from about 1 carbon atom to about 10 carbon atoms, such as dimethylolphenols or phenolic resins substituted with alkyl groups having from about 1 carbon atom to about 10 carbon atoms in the para position. In some embodiments, a blend of octylphenol-formaldehyde and nonylphenol-formaldehyde resins is employed. The blend comprises about 25 wt% to about 40 wt% octylphenol-formaldehyde and about 75 wt% to about 60 wt% nonylphenol-formaldehyde, for example about 30 wt% to about 35 wt% octylphenol-formaldehyde and about 70 wt% to about 65 wt% nonylphenol-formaldehyde. In some embodiments, the blend comprises about 33 wt% octylphenol-formaldehyde and about 67 wt% nonylphenol-formaldehyde resin, each of the octylphenol-formaldehyde and nonylphenol-formaldehyde comprises a methylol group. The blend can be solubilized in paraffinic oil at about 30% solids without phase separation.

[0165] Useful phenolic resins are available under the trade designations SP-1044, SP-1045 (Schenectady International; Schenectady, NY), which are sometimes referred to as alkylphenol-formaldehyde resins.

[0166]

[0161] Examples of phenolic resin curing agents include those defined according to the following general formula:

[0167] [ka]

[0168] wherein Q is a divalent radical selected from the group consisting of -CH2-, -CH2-O-CH2-; m is zero or a positive integer from 1 to 20, and R' is an organic group. In some embodiments, Q is the divalent radical -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 radical having 4 to 12 carbon atoms.

[0169] In some embodiments, the phenolic resin is used in combination with a halogen source, such as stannous chloride, and a metal oxide or reducing compound, such as zinc oxide.

[0170] Other Ingredients Other ingredients may be added at one or more locations along the extruder and / or at the feed throat. In some embodiments, the TPV composition may include a polymer processing additive. The processing additive may be a polymeric resin with a very high melt flow index. These polymeric resins include both linear and branched polymers with melt flow rates of about 500 dg / min or greater, such as about 750 dg / min or greater, such as about 1000 dg / min or greater, such as about 1200 dg / min or greater, such as about 1500 dg / min or greater. Mixtures of various branched or various linear polymer processing additives, as well as mixtures of both linear and branched polymer processing additives, may be employed. References to polymer processing additives may include both linear and branched additives unless otherwise specified. Linear polymer processing additives include polypropylene homopolymers and branched polymer processing additives include diene modified polypropylene polymers. TPV compositions containing similar processing additives are disclosed in US Pat. No. 6,451,915, which is incorporated herein by reference for purposes of United States patent practice.

[0171] In some embodiments, the TPV compositions of the present disclosure may optionally include reinforcing and non-reinforcing fillers, compatibilizers, antioxidants, stabilizers, rubber processing oils, lubricants, antiblocking agents, antistatic agents, waxes, blowing agents, pigments, flame retardants, nucleating agents, and other processing aids known in the rubber compounding art. These additives may be used in the TPV composition in amounts up to about 50 wt% of the total weight of the TPV composition.

[0172]

[0165] Fillers and extenders that can be utilized include conventional inorganic materials such as calcium carbonate, clay, silica, talc, titanium dioxide, carbon black, nucleating agents, mica, wood flour, and the like, and blends thereof, as well as nanoscale inorganic and organic fillers.

[0173] In some embodiments, the TPV composition may include a plasticizer, such as an oil, such as a mineral oil, a synthetic oil, an ester plasticizer, or a combination thereof. These oils may also be referred to as plasticizers or extenders. Mineral oils may include aromatic oils, naphthenic oils, paraffinic oils, isoparaffinic oils, synthetic oils, and combinations thereof. In some embodiments, the mineral oils may be treated or untreated. Useful mineral oils may be obtained under the trade name SUNPAR™ (Sun Chemical). Other oils are available under the trade names PARALUX™ (Chevron), and PARAMOUNT™ (Chevron), such as Paramount™ 6001R (Chevron Phillips). Other oils that may be used include hydrocarbon oils and plasticizers, such as organic esters and synthetic plasticizers. Many additive oils are derived from petroleum fractions and have specific ASTM designations depending on whether they fall into the paraffinic, naphthenic, or aromatic oil classes. Other types of additive oils include alpha-olefin based synthetic oils, such as liquid polybutylene.Additive oils other than petroleum based oils can also be used, examples of which include oils derived from coal tar and pine tar, as well as synthetic oils, such as polyolefin materials.

[0174]

[0167] Examples of oils include base stocks. According to the American Petroleum Institute (API) classification, base stocks are categorized into five groups based on their saturated hydrocarbon content, sulfur level, and viscosity index (Table 6). Lubricating oil base stocks are typically produced on a large scale from non-renewable petroleum sources. Group I, II, and III base stocks are all obtained from crude oil by large-scale processing such as solvent extraction, solvent or catalytic dewaxing, and hydroisomerization, hydrocracking, and isodewaxing, isodewaxing, and hydrofinishing. See, "New Lubes Plants Use State-of-the-Art Hydrodewaxing Technology," Oil & Gas Journal, September 1, 1997; Krishna et al., "Next Generation Isodewaxing and Hydrofinishing Technology for Production of High Quality Base Oils," 2002 NPRA Lubricants and Waxes Meeting, November 14-15, 2002; Gedeon and Yenni, "Use of "Clean" Paraffinic Processing Oils to Improve TPE Properties," presented at TPES 2000, Philadelphia, PA, September 27-28, 1999.

[0175] Group III base stocks can also be produced from synthetic hydrocarbon liquids obtained from natural gas, coal or other fossil sources, Group IV base stocks are polyalphaolefins (PAOs) and are produced by 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 naphthenics, polyalkylene glycols (PAGs), and esters.

[0176] [Table 5]

[0177]

[0169] In some embodiments, the Group II base stock contains a total amount of aromatic and polar compounds, based on the total weight of the base stock, of greater than about 4.5 wt.%, or less than about 4.5 wt.%, as measured in accordance with ASTM 2007, and / or the viscosity of the oil is at least about 80 cSt at 40°C.

[0178]

[0170] In some embodiments, the mineral oil may have a viscosity of at least 10 cSt at 100°C.

[0179]

[0171] In some embodiments, the oil may contain less than about 4 wt.% aromatic compounds and / or less than about 0.3 wt.% polar compounds, based on the total weight of the oil, as measured according to ASTM 2007.

[0180]

[0172] In some embodiments, synthetic oils include polymers and oligomers of butene. For example, synthetic oils may be oligomers of 1-butene. In some embodiments, the oligomeric form of synthetic oils can be characterized by a number average molecular weight (Mn) of about 300 g / mol to about 9,000 g / mol, and in other embodiments, about 700 g / mol to about 1,300 g / mol. In some embodiments, these oligomers include isobutenyl units. Exemplary synthetic oils include polyisobutylene, poly(isobutylene-co-butene), and mixtures thereof. In some embodiments, synthetic oils can include polylinear α-olefins, polybranched α-olefins, hydrogenated polyalphaolefins, and mixtures thereof.

[0181] In some embodiments, the synthetic oils include synthetic polymers or copolymers having a viscosity of about 20 cps or greater, e.g., about 100 cps or greater, e.g., about 190 cps or greater, as measured by a Brookfield viscometer according to ASTM D-4402 at 38° C. In these or other embodiments, the viscosity of these oils may be about 4,000 cps or less, e.g., about 1,000 cps or less.

[0182]

[0174] In some embodiments, the oil has less than 3 wt% DMSO extractable as measured according to IP-346.

[0183] Useful synthetic oils may be obtained commercially under the trade names Polybutene™ (Soltex; Houston, Texas), and Indopol™ (Ineos). White synthetic oils are available under the trade names SPECTRASYN™ (ExxonMobil), formerly named SHF Fluids (Mobil), Elevast™ (ExxonMobil), and white oils produced by liquid fuel synthesis technology, such as Risella™ X415 / 420 / 430 (Shell) or the Primol™ (ExxonMobil) series of white oils, such as Primol™ 352, Primol™ 382, ​​Primol™ 542, or Marcol™ 82, Marcol™ 52, the Drakeol™ (Pencero) series of white oils, such as Drakeol™ 34, or combinations thereof. The oils described in US Pat. No. 5,936,028 may also be employed.

[0184]

[0176] Overall, the present disclosure provides an extrusion method and extruder system capable of providing a TPV composition with enhanced processability and enhanced surface properties using less filler. The extruder system and process of the present disclosure can introduce a thermoplastic polymer separate from the rubber to provide the TPV composition.

[0185]

[0177] Unless otherwise specified, the phrases "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned in this specification, so long as such steps, elements, or materials do not affect the basic and novel characteristics of the present disclosure, and in addition, they do not exclude impurities and differences normally associated with the elements and materials used.

[0186]

[0178] For the purpose of brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit can be combined with any upper limit to enumerate a range that is not explicitly recited, and in addition, a range from any lower limit can be combined in the same manner with any other lower limit to enumerate a range that is not explicitly recited, and any upper limit range can be combined with any other upper limit to enumerate a range that is not explicitly recited. In addition, a range includes every point or individual value between its endpoints, even if not explicitly recited. Thus, every point or individual value can itself serve as a lower limit or upper limit to be combined with every other point or individual value or any other lower limit or upper limit to enumerate a range that is not explicitly recited.

[0187]

[0179] All numerical values ​​within the detailed description herein are modified by the stated value being "about" to take into account experimental error and variations that would be expected by one of ordinary skill in the art.

[0188]

[0180] All documents described herein are incorporated by reference herein, including any priority documents and / or test procedures, to the extent that they are not inconsistent with this specification. As is apparent from the general description and specific embodiments above, the forms of the disclosure have been illustrated and described, but various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, the disclosure is not intended to be limited thereby. Similarly, the term "comprising" is considered synonymous with the term "including" for purposes of U.S. law. Similarly, it is understood that whenever a composition, element, or group of elements is followed by the transition phrase "comprising," the same composition or group of elements is also contemplated when the composition, element, or list of elements is followed by the transition phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "is," and vice versa.

[0189]

[0181] While the present disclosure has been described with respect to numerous embodiments and examples, those skilled in the art will recognize that, having the benefit of this disclosure, they may devise other embodiments which do not depart from the scope and spirit of the present disclosure.

Claims

1. 1. A method for forming a dynamically crosslinked thermoplastic elastomer (TPV) composition, comprising: introducing a thermoplastic polymer into the extruder via a feed throat; introducing an elastomeric polymer into a melt feeder to form an elastomeric polymer melt comprising the elastomeric polymer, the melt feeder being coupled to the extruder; introducing the elastomeric polymer melt from the melt feeder into the extruder, wherein the thermoplastic polymer and the elastomeric polymer melt are fed separately into the extruder; and mixing the thermoplastic polymer and the elastomeric polymer melt in the extruder using a plurality of intermesh screws, the extruder comprising a plurality of mixing sections; The above method, comprising:

2. 10. The method of claim 1, wherein the plurality of mixing sections comprises at least three mixing sections, at least one of the mixing sections having a greater mixing intensity than another of the at least three mixing sections.

3. 3. The method of claim 2, wherein the second mixing section has a greater mixing intensity than a first mixing section upstream of the second mixing section and a third mixing section downstream of the second mixing section of the at least three mixing sections.

4. 3. The method of claim 1 or 2, wherein the mixing intensity of the mixing section located in the first one-half to three-quarters of the length of the extruder is greater than the mixing intensity of mixing sections located along other lengths of the extruder.

5. The melting of the thermoplastic and elastomeric polymers A first one of the plurality of mixing sections is mixed for about 1000 seconds. －１ ~about 1800 seconds －１ operating at a dynamic mixing intensity of; A second one of the plurality of mixing sections is mixed for about 1200 seconds. －１ ~about 2100 seconds －１ operating at a dynamic mixing intensity of; A third of the plurality of mixing sections is mixed for about 3100 seconds. －１ ~about 5600 seconds －１ and operating at a dynamic mixing intensity of A fourth of the plurality of mixing sections is mixed for about 1,100 seconds. －１ ~Approx. 1,900 seconds －１ Operate at a dynamic mixing intensity of and wherein each of the first, second, third and fourth sections are in sequence with one another from the upstream end to the downstream end of the extruder.

6. mixing the thermoplastic polymer and the elastomeric polymer melt; operating a first section of the plurality of mixing sections at an effective mixing intensity of about 80 to about 160; operating a second one of the plurality of mixing sections at an effective mixing intensity of about 110 to about 190; operating a third of the plurality of mixing sections at an effective mixing intensity of about 290 to about 450; and operating a fourth of the plurality of mixing sections at an effective mixing intensity of about 90 to about 170.

3. The method of claim 1, wherein each of the first, second, third and fourth sections are in sequence with one another from the upstream end to the downstream end of the extrusion.

7. 3. The method of claim 1 or 2, wherein the thermoplastic polymer is introduced at a first location and the elastomeric polymer melt is introduced at a second location, the second location being downstream of the first location, and the first and second locations being each located in the first one-sixteenth to one-quarter of the length of the extruder.

8. 8. The method of claim 7, further comprising introducing a curative into the extruder at a third location in the extruder, the third location being located downstream of the first and second locations, the third location being located in the first one-third to two-thirds of the length of the extruder.

9. 3. The method of claim 1 or 2, further comprising the step of introducing a powder blend comprising a cure moderator and a filler into the extruder through the feed throat.

10. 10. The method of claim 9, wherein the filler comprises a material selected from the group consisting of calcium carbonate, clay, silica, talc, titanium dioxide, carbon black, nucleating agents, mica, wood flour, nanoscale inorganic fillers, nanoscale organic fillers, and combinations thereof.

11. The method of claim 9 , wherein the cure moderator comprises a phenolic resin.

12. 3. The method of claim 1 or 2, wherein the thermoplastic polymer is selected from the group consisting of polypropylene homopolymer, polyethylene homopolymer, propylene ethylene copolymer, and combinations thereof.

13. The method of claim 1 or 2, wherein the elastomeric polymer comprises an ethylene propylene diene terpolymer.

14. 3. The method of claim 1 or 2, further comprising the step of injecting process oil at one or more locations along the extruder.

15. The process oil is a paraffin-based oil, the process oil is injected via one or more liquid pumps coupled to the extruder; 15. The method of claim 14, wherein the process oil is injected upstream of, downstream of, or upstream and downstream of the curative introduced into the extruder.

16. 3. The method of claim 1 or 2, wherein forming the elastic polymer melt in the melt feeder is carried out at a temperature of from about 90°C to about 120°C.

17. 3. The method of claim 1 or 2, further comprising the step of introducing a powder blend including a cure moderator and a filler into the feed throat, the powder blend being introduced in an amount of from about 1 part to about 4 parts per 100 parts rubber.

18. 18. The method of claim 17, wherein the cure moderator is introduced into the feed throat in an amount of from about 0.5 parts to about 2.0 parts per 100 parts rubber.

19. 20. The method of claim 18, wherein the cure moderator is selected from the group consisting of stannous chloride, zinc oxide, and combinations thereof.

20. The method of claim 1 or 2, wherein the thermoplastic polymer is introduced into the feed throat in an amount of from about 7 parts to about 100 parts per 100 parts rubber.

21. 15. The method of claim 14, wherein the processing oil is introduced in an amount of from about 25 parts to about 41 parts per 100 parts rubber.

22. The method of claim 8, wherein the curative is introduced in an amount of from about 3 parts to about 10 parts per 100 parts of rubber.

23. 3. The method of claim 1 or 2, further comprising providing an extrudate formed from the thermoplastic polymer and the elastomeric polymer melt from the extruder to a twin-screw melt pump to form a composition, and removing the composition from the twin-screw melt pump.

24. 3. The method of claim 1, wherein the step of mixing the thermoplastic polymer and the elastomeric polymer melt in the extruder is carried out at a total effective mixing intensity of about 690 to about 830.

25. The step of mixing the thermoplastic polymer and the elastomeric polymer melt in the extruder may be performed for about 7,000 seconds. －１ ~Approx. 12,000 seconds －１ 3. The method of claim 1, wherein the total dynamic mixing intensity is

26. 3. The method of claim 1, wherein the step of mixing the thermoplastic polymer and the elastomeric polymer melt in the extruder is carried out at an average extrusion temperature of about 160°C to about 320°C.

27. 3. The method of claim 1 or 2, wherein the TPV composition has an extrusion surface roughness (ESR) of about 25 μin to about 50 μin.

28. 3. The method of claim 1 or 2, wherein the TPV composition has a head pressure drop of about 40% or less compared to a control composition made by simultaneously introducing the thermoplastic polymer and the elastomeric polymer into the extruder.

29. 3. The method of claim 1 or 2, wherein the TPV composition contains about 23 or fewer surface spots using visual observation of three strips.

30. 1. An extruder system comprising: an extrusion having a first end, a second end, and a plurality of ports disposed along the extruder; a feed port at a first end of the extruder connected to a first port of the plurality of ports; a melt feeder coupled to a second port of the plurality of ports downstream of the first port; a hardener source coupled to a third port of the plurality of ports, the third port being positioned downstream or upstream of the second port; and a melt pump connected to the second end of the extruder. an extruder system including:

31. 31. The extruder system of claim 30, wherein a process oil pump is coupled to a fourth port of the plurality of ports, upstream or downstream of the third port.

32. 1. A method for forming a dynamically crosslinked thermoplastic elastomer (TPV) composition, comprising: introducing a thermoplastic polymer into the extruder through a feed throat at a first location; introducing an elastomeric polymer into a melt feeder to form an elastomeric polymer melt comprising the elastomeric polymer, the melt feeder being coupled to the extruder; introducing the elastomeric polymer melt from the melt feeder into the extruder at a second location downstream from the first location; and mixing the thermoplastic polymer and the elastomeric polymer melt in the extruder using a plurality of intermesh screws. The above method, comprising:

33. 33. The method of claim 32, wherein the thermoplastic polymer is selected from the group consisting of polypropylene homopolymer, polyethylene homopolymer, propylene ethylene copolymer, and combinations thereof.

34. 34. The method of claim 32 or 33, wherein the elastomeric polymer comprises an ethylene propylene diene terpolymer.