thermoplastic compositions, methods, apparatus and uses

专利摘要:
thermoplastic polyurethane (tpu) compositions, methods for producing tpu compositions, methods of using tpu compositions and apparatus produced therefrom are disclosed. the disclosed tpu compositions include a thermoplastic polyurethane polymer, a heat stabilizer, a flow agent and a reinforcing material. the reinforcement can be a fiberglass. the disclosed tpu compositions have improved thermal stability and improved flow properties, suitable for injection molding of articles of manufacture that have a large plurality of openings or fine pores. articles produced from the composition have superior thermal stability, abrasion resistance and chemical resistance. exemplary articles include screening members for vibrating screening machines.
公开号:BR112019022586A2
申请号:R112019022586
申请日:2018-04-27
公开日:2020-05-19
发明作者:R Colgrove James；Wojchiechowski Keith
申请人:Derrick Corp；
IPC主号:

专利说明:

APPARATUS, METHODS AND SYSTEMS FOR VIBRATING SCREENING
[0001] This application claims the benefit of the Provisional Patent Applications with serial numbers US 62 / 492,054, filed on April 28, 2017, and US 62 / 500,262, filed on May 2, 2017, the entire content of which is incorporated into the this document as a reference, and whose priority is claimed in this document.
SUMMARY OF DRAWINGS
[0002] Figure 1 is an isometric top view of a sieve element, according to one embodiment.
[0003] Figure 1A is a top view of the sieve element shown in Figure 1, according to an embodiment.
[0004] Figure 1B is a lower isometric view of the sieve element shown in Figure 1, according to an embodiment.
[0005] Figure 1C is a bottom view of the sieve element shown in Figure 1, according to an embodiment.
[0006] Figure 2 is an enlarged top view of a rupture portion of the sieve element shown in Figure 1, according to an embodiment.
[0007] Figure 3 is an isometric view of a final subgrade that shows the sieve elements before fixing to the final subgrade, according to one modality.
[0008] Figure 3A is an exploded isometric view of the final subgrade shown in Figure 3, which has the sieve elements attached to it, according to one embodiment.
[0009] Figure 4 illustrates an exemplary sieving assembly, which was generated from sieving members and subgrade structures, as described below, with reference to Figures 1 to 3A, according to an embodiment.
[0010] Figure 5 illustrates the results of the actual field tests of the screening assemblies, according to one modality.
DESCRIPTION OF MODALITIES
[0011] This revelation, in general, refers to the compositions, the devices,
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2/35 to the methods and uses of thermoplastic polyurethanes (TPU). TPU compositions of the disclosed modality can be used in injection molding processes to generate screening members for use in vibrating screening machines. Vibratory sorting machines provide an ability to excite an installed sieve, so that the materials placed on the sieve can be separated to a desired level. Oversized materials are separated from undersized materials. The disclosed compositions and sieving members can be used in areas of technology related to the oil industry, gas / oil separation, mining, water purification and other related industrial applications.
[0012] The disclosed modalities provide sieving members that meet demand requirements, such as: fine openings from approximately 43 pm to approximately 100 pm, which effectively sieve particles of similar size; large area sieves of the order of several square meters (square feet), with a large open sieving area, of the order of 30% to 35%; sieves that are thermally and mechanically stable, which can withstand adverse conditions during operation, such as compression loading (eg forces from 680 kg (1,500 pounds) to 11,360 kg (3,000 pounds), applied to the edges of the sieving members and accelerations vibrational vibrations of up to 98 m / s (10 G)) and loading of high temperature materials (for example, between 37 ° C and 94 ° C), with significant weight loads and adverse chemical and abrasive conditions of the materials being screened.
[0013] The materials and methods of the revealed modality provide a hybrid approach, in which small screening elements are micro-molded using revealed TPU materials to reliably generate fine resources on the order of 43 pm to approximately 100 pm to produce screening elements that have a large open screening area. The TPU materials disclosed, as discussed in more detail below, include modalities that feature optimized amounts of reinforcement, heat stabilizer and flow agent as additives to the thermoplastic polyurethane
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3/35 appropriate. These additives, in turn, allow small sieve elements to be securely attached, such as by laser welding, to the subgrade structures, to provide mechanical stability that can withstand the large mechanical loads and accelerations mentioned above. For example, glass fibers can be used as reinforcement material, which allows the strengthening of the TPU material and, in turn, allows the screen elements to be securely attached to the subgrade structures with greater structural stability. . However, the addition of large quantities of glass fibers can lead to increasing difficulty in laser welding, since the refractive properties of glass provide obstacles to laser systems. Any amount of additive will also necessarily require dilution of the thermoplastic urethane. Likewise, a minimal but effective amount of heat stabilizer must be added, in which the additive must have a sufficient amount to allow the final structure to support the addition of high temperature materials, as described above.
[0014] As discussed in more detail below, the amount of additives in the disclosed TPU compositions may also vary based on the desired T thickness of the sieve element surface elements, as discussed in detail in US Patent Applications 15 / 965,195 and US 62 / 648,771, which are hereby incorporated by reference. For example, as discussed in US Patent Application No. 15 / 965,195, in Paragraphs [00366] to [00373] and in corresponding Tables 1 to 4, the thickness T of the sieve element surface elements can vary in an effort to maximize the percentage of open area in the general sieve assembly, which allows greater efficiency of the sieve assembly, when in use.
[0015] A plurality of these optimized subgrade structures can then be mounted on screening structures with large surface areas, in the order of several square meters (square feet). Sieve assemblies, based on the disclosed TPU compositions, can be used, for example, in the manner described in U.S. Patent Applications No. 15 / 965,195 and U.S.
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62 / 648,771. For example, as described in Patent Application No. US 15 / 965,195, in Paragraphs [0017] to [0021] of the Descriptive Report, the grid frame, based on the revealed TPU compositions, can provide the necessary durability against damage or deformation under the impacts of the substantial vibratory load to which it is subjected when attached to a vibrating screening machine. The subgrades, when assembled to form the complete sieve assembly, are strong enough, not only to withstand the forces necessary to secure the sieve assembly to the vibrating sieving machine, but also to withstand the extreme conditions that may be present in the loading vibrating. As discussed in detail, in paragraphs [00280] to [00282] of US Patent Specification No. 15 / 965,195, a preferred method of gripping the screen elements in the subgrade may include laser welding of the melt bars arranged in the subgrades. The disclosed TPU compositions, for that reason, can be used to create the referenced vibrating screening apparatus, capable of withstanding the extreme conditions discussed in this document and in U.S. Patent Application No. 15 / 965,195.
[0016] Screen assemblies based on the disclosed TPU compositions can also be configured to be mounted on vibrating screening machines described in U.S. Patent No. 7,578,394; U.S. 5,332,101; U.S. 6,669,027; U.S. 6,431,366; and U.S. 6,820,748. Such sieve assemblies may include: side portions or binder bars that include U-shaped members configured to receive tensioning members of the over-mount type, as described in U.S. Patent No. 5,332,101; side portions or binder bars that include finger receiving openings configured to receive mounting-type tensioning, as described in U.S. Patent No. 6,669,027; side members or binders for compression loading, as described in U.S. Patent No. 7,578,394; or it can be configured for fixing and loading on multi-layer machines, such as the machines described in U.S. Patent No. 6,431,366.
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[0017] Screen assemblies and / or screening elements, based on the revealed TPU compositions, can also be configured to include the features described in US Patent No. 8,443,984, which includes guide assembly technologies, described in this document, and the preformed panel technologies described in this document. In addition, in addition, the screen assemblies and the screening elements, based on the revealed TPU compositions, can be configured to be incorporated into the pre-screening technologies, compatible with assembly structures and the screen configurations, described in Patents no. US 5,332,101; U.S. 4,882,054; U.S. 4,857,176; U.S. 6,669,027; U.S. 7,228,971; U.S. 6,431,366; U.S. 6,820,748; U.S. 8,443,984; and U.S. 8,439,203. The disclosure of each of these patent documents, together with their families and related patent applications, and the patents and patent applications mentioned in these documents, are expressly incorporated by reference in their entirety for reference, in their entirety.
EXEMPLIFICATIVE SCREENING MODALITIES
[0018] Screening members, manufactured from hot-curing polymers and thermoplastics, are described in the patent documents mentioned above (ie, Provisional Patent Application Serial No. US 61 / 652,039 and US 61 / 714,882 ; US Patent Application No. 13 / 800,826; US Patent No. 9,409,209; US Patent No. 9,884,344; and US Patent Application 15 / 851,099), the disclosures of which are incorporated herein, to reference title in its entirety.
[0019] Figures 1 to 3A illustrate the examples of sieving modalities generated by injection molding processes, using revealed TPU compositions. Figures 1 to 1C show a 416 element sieve element, which has substantially parallel sieve element end portions 20 and substantially parallel sieve element side portions 22, which are substantially perpendicular to the sieve element end portions 20 The 416 sieve element
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6/35 may include a plurality of tapered counter-holes 470, which can facilitate the extraction of the sieve element 416 from a mold, as described in more detail in the patent documents mentioned above. The sieve element 416 can additionally include location openings 424, which can be located in the center of the sieve element 416 and in each of the four corners of the sieve element 416. Location openings 424 are useful for securing the sieve element 416 to the subgrade structures, as described in more detail below, with reference to Figures 3 and 3A.
[0020] As shown in Figures 1 and 1A, the sieve element 416 has a sieve surface 13 that includes solid surface elements 84 that extend parallel to the end portions of the sieve element 20 and that form sieve openings. 86, as also shown in the foreground view of Figure 2, as described in more detail below.
[0021] Figures 1B and 1C show a bottom view of the sieve element 416, which has a first sieve element support member 28 that extends between the end portions 20 and which is substantially perpendicular to the end portions 20. Figure 1B also shows a second screen element support member 30, perpendicular to the first element support member 28 which extends between the side edge portions 22, which is approximately parallel to the end portions 20 and which is substantially perpendicular to the side portions 22. The sieve element may additionally include a first series of reinforcement members 32, substantially parallel to the side edge portions 22, and a second series of reinforcement members 34, substantially parallel to the end portions 20. The portions end 20, the side edge portions 22, the first screen support member 28, the second screen support member ra 30, the first series of reinforcement members 32 and the second series of reinforcement members 34 structurally stabilize the sieve surface elements 84 and the sieve openings 86 during various loads, which includes the distribution of a compressive force and / or vibratory loading conditions.
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[0022] As shown in Figures 1B and 1C, the sieve element 416 may include one or more adhesion arrangements 472, which may include a plurality of extensions, cavities or a combination of extensions and cavities. In this example, the adhesion arrangement 472 is a plurality of cavity pockets. Adhesion provision 472 is configured to correspond to the complementary adhesion provisions of a subgrade structure. For example, the subgrade structure 414 (shown in Figures 3 and 3A) has a plurality of melting bars, 476 and 478, which correspond to the cavity pockets 472 of the sieve element 416, as described in more detail below, with reference Figures 3 and 3A.
[0023] As shown in Figure 2, the screening openings 86 can be elongated slits having a length L and a width W, separated by surface elements 84 having a thickness T. The thickness T can vary, depending on the application of sieving and sieve opening configuration 86. Thickness T can be chosen to be approximately 76 pm to] 508 pm (ie, about 0.003 inches to about 0.020 inches), depending on the desired open sieving area and the width W of the sieving apertures 86. In an exemplary embodiment, the thickness T of the surface elements can be 381 pm (i.e., 0.015 inches). However, the properties of the disclosed TPU compositions allow for the formation of thinner surface elements, such as surface elements that have a T thickness of 177.8 pm (i.e., 0.007 inches). The smaller the thickness T, of the surface elements, the greater the sieving area of the sieve element. For example, a T thickness of 356 pm (0.014 inches) will provide a sieve element that is about 10 to 15% open, while a T thickness of 76 pm (0.003 inches) will provide a sieve element that is about 30 to open. 35% open, thereby increasing the open sieving area.
[0024] As mentioned above, the screening apertures 86 have a width W. In exemplary embodiments, the width W may be
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8/35 approximately 38 pm to approximately 150 pm (i.e., about 0.0015 to 0.0059 inches) between the inner surfaces of each element of the screen surface 84. The length-to-width ratio of the openings can be 1 : 1 (ie, corresponding to rounded pores) to 120: 1 (ie, long narrow slits). In exemplary embodiments, the openings may preferably be rectangular and may have a length / width ratio between about 20: 1 (e.g., length 860 pm; width 43 pm) to about 30: 1 (i.e., length about 1,290 pm and width about 43 pm). The sieving openings need not be rectangular, but can be molded by thermoplastic injection to include any suitable shape in a specific sieving application, which includes approximately square, circular and / or oval.
[0025] As described in more detail below, for greater stability, the surface elements of the sieve 84 may include integral fiber materials (e.g., glass fibers) that can extend substantially parallel to the end portions 20. The sieve element 416 can be a single thermoplastic injection molded piece. Screen element 416 may also include several injection molded thermoplastic parts, each configured to cover one or more grid openings. The use of small injection molded thermoplastic sieve elements 416, which are attached to a grid frame, as described below, provides substantial advantages over previous sieve assemblies, as described in more detail in the aforementioned patent documents.
[0026] Figures 3 and 3A illustrate a process for fixing the sieve elements 416 in a final subgrade unit 414, according to an embodiment. The screen elements 416 can be aligned with the final subgrade unit 414 through the elongated fastening members 444 (from the subgrade 414) that engage the location openings 424 at the bottom of the screen element 416 (for example, see Figures 1 to 1C). In this regard, the elongated fastening members 444 of the subgrade 414 pass into the sieve element locating openings 424 of the sieve element 416. The members
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Elongated fastening clips 9/35 444 of the final subgrade 414 can then be cast to fill the tapered holes of the fixing holes of the screen element 424, thereby attaching the screen element 416 to the subgrade unit 414. A fixing through the elongated fixing members 444 and the sieve element locating openings 424 is only one method for fixing the sieve member 416 to the subgrade 414.
[0027] Alternatively, the sieve element 416 can be attached to the final subgrade unit 414 using adhesives, fasteners and fastener openings, laser welding, etc. As described above, melting bars 476 and 478, from subgrade 414 (for example, see Figures 3 and 3A), can be configured to fit into the pockets of cavity 472 of the sieve element 416 (for example, see Figures 1 to 3C). By applying heat (for example, by laser welding, etc.), the melting bars 476 and 478 can be fused to form a connection between the sieve element 416 and the subgrade 414, after cooling.
[0028] The arrangement of the sieve elements 416 in subgrades (for example, subgrade 414), which can also be molded by thermoplastic injection, allows the easy construction of sieve assemblies complete with very fine sieve openings. The arrangement of the sieve elements 416 in subgrades also allows for substantial variations in the overall size and / or configuration of the sieve assembly 10, which can vary, which includes larger or smaller subgrades, or subgrades with different shapes, etc. In addition, a screen assembly can be constructed with a variety of screen opening sizes, or a gradient of screen opening sizes simply by incorporating screen elements 416, with screen screens of different sizes in subgrades and by joining the subgrades to form the desired configuration.
[0029] The sieves described above, with reference to Figures 1 to 3, and revealed in the reference patent documents above, have small sieving openings, suitable for use as sieving members. At
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10/35 revealed TPU compositions additionally allow these screens to work effectively in each of the following key areas: structural stability and durability; ability to withstand loading of the compression type; ability to withstand high temperatures; extended service life, despite potential abrasions, cuts or tears; and manufacturing methods that are not overly complicated, time-consuming or error-prone.
There is, therefore, a need for improved TPU compositions, which have improved chemical properties, which can be formed by means of injection molding in sieving members, and sieve assemblies, which have improved physical properties.
[0031] The disclosed compositions, in general, include a TPU material, a heat stabilizer, selected to optimize the heat resistance of the composition, a flow agent, selected to optimize the use of the composition in injection molding, and a reinforcement material, selected to optimize the stiffness of the resulting composite material. The reinforcement can be included in an amount of less than about 10% by weight of the TPU. In one embodiment, the reinforcement is provided in an amount of about 7% by weight of the TPU. In other exemplary embodiments, the reinforcement is provided in amounts of less than about 7%, less than about 5% or less than about 3% of the TPU weight.
[0032] An example of a reinforcement material includes glass fibers. Glass fibers can be introduced in an amount that allows the use of the composition in injection molding, improves the stiffness of the composition by hardening, increases the temperature resistance of the final product, and also does not prevent laser welding, from composition, in other materials.
[0033] An initial length of glass fibers can be between about 1.0 mm and about 4.0 mm. In one embodiment, the glass fibers have an initial length of about 3.175 mm (i.e., 1/8 inch). Glass fibers can also have a diameter of less than about 20 pm, such as between about 2 pm and about 20 pm. In an exemplary embodiment, the glass fibers have a diameter between about 9 pm and about 13 pm.
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[0034] The TPU material can be produced from a low free isocyanate monomer prepolymer. In an exemplary embodiment, the low content free isocyanate monomer prepolymer can be chosen to be p-phenylene diisocyanate. In additional embodiments, other prepolymers can be chosen. TPU can be generated first by reacting a urethane prepolymer with a curing agent. The urethane prepolymer can be chosen to have a free polyisocyanate monomer content of less than 1% by weight.
[0035] The resulting material can then be thermally processed by extrusion, at temperatures of 150 ° C, or more, to form the TPU polymer. The urethane prepolymer can be prepared from a polyisocyanate monomer and a polyol that includes alkane diol, polyether polyol, polyester polyol, polycaprolactone polyol and / or polycarbonate polyol. In an exemplary embodiment, the curing agent can include a diol, a triol, a tetrol, an alkylene polyol, a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a diamine or a diamine derivative.
[0036] According to one embodiment, the heat stabilizer, mentioned above, can be included in an amount of about 0.1% to about 5% by weight of the TPU. The heat stabilizer can be a sterically hindered phenolic antioxidant. The sterically hindered phenolic antioxidant may be pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (CAS registry 6683-19-8). Optionally, an ultraviolet (UV) light stabilizer can be included. In some embodiments, the heat stabilizer will also serve as a UV light stabilizer.
[0037] According to one embodiment, the flow agent, mentioned above, can be included in an amount of about 0.1% to about 5% by weight of the TPU. The flow agent can be chosen to be a sterile ethylene wax. Ethylene ester wax may include octadecanamide, N, N'-1,2ethanedi-ylbis (CAS record 110-30-5) and stearic acid (CAS record 57-11-4). In other embodiments, other flow agents can be chosen.
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[0038] According to one embodiment, the glass fibers, mentioned above, can have a diameter or width between about 2 and about 20 pm, between about 9 and about 13 pm, or can have a diameter or a width of about 11 pm. The glass fibers can have an initial length between about 3.1 mm and about 3.2 mm. An average final length of the glass fibers, in a hardened state after injection molding, can be less than about 1.5 mm, due to fiber breakage during processing. In a final hardened state, after injection molding. , the fibers can be characterized by a distribution of lengths ranging from about 1.0 mm to about 3.2 mm, with some fibers remaining intact.
[0039] The disclosed modalities include methods of production and use of TPU compositions suitable for use in the injection molding of articles of manufacture that have fine pores. The methods of the modality include promoting the reaction of a TPU, a heat stabilizer, a flow agent and a reinforcing material, at a temperature above about 150 ° C, to generate a TPU composition. The reinforcement may include a glass fiber that has a diameter between about 2 pm and about 20 pm, in an amount selected to optimize the stiffness of the articles fabricated from the TPU composition. The TPU can be polycarbonate TPU. TPU can be a prepolymer before the reaction step. The glass fiber can be present in an amount between about 1% and about 10% by weight of the TPU. In one embodiment, the fiberglass may be present in an amount of about 7% by weight of the TPU.
[0040] The articles of manufacture molded from the compositions disclosed in this document are suitable to be joined by various methods, including laser welding. In this regard, the resulting articles can be laser welded to other articles, such as support structures.
[0041] Exemplary articles of manufacture include members for shaker vibrating screens, as described above. The disclosed TPU material, described above, can then be used in an injection molding process to generate a sieving member. In this regard, the
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TPU can be inserted / injected into a properly designed mold, at an elevated temperature. The temperature can be chosen to be a temperature at which the TPU material has a sufficiently low viscosity to allow the material to flow into the mold. After cooling, the resulting solidified sieving member can be removed from the mold.
[0042] The resulting sieving member can be designed to have a plurality of openings having opening widths ranging from 38 pm to about 150 pm. Sieves with such openings can be used to remove particles from various industrial fluids to filter / clean fluids. Particles that are larger than the widths of the screening apertures can be removed effectively. The desirable thermal properties of the TPU material allow the screening members produced from the TPU material to effectively sieve particles at elevated temperatures (for example, service temperatures up to about 82 to 94 ° C).
[0043] The characteristics of the revealed TPU compositions, and products generated from it, include temperature and flow characteristics that facilitate the production of very fine, high-resolution structures using techniques such as injection molding. The resulting end products also have excellent thermal stability at elevated operating temperatures (for example, up to about 94 ° C. The resulting structures also exhibit sufficient structural rigidity to withstand compression loading, while maintaining small openings that allow the screening of particulate material. in micron scale The structures generated from materials and TPU also exhibit cut, tear and abrasion resistance, as well as chemical resistance in hydrocarbon rich environments (for example, environments that include hydrocarbons, such as diesel oil).
THERMOPLASTIC POLYURETHANES
[0044] The disclosed modalities provide thermoplastic compositions that include polyurethanes, which are a class of macromolecular plastics known as polymers. In general, polymers, such as polyurethanes, include
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14/35 smaller, repetitive units, known as monomers. Monomers can be chemically linked from end to end to form a primary long chain primary molecule, with or without attached side groups. In an exemplary embodiment, polyurethane polymers can be characterized by a main molecular structure that includes carbonate groups (-NHCO2), for example.
[0045] Although, in general, categorized as plastics, thermoplastic compositions include polymer chains that are not covalently linked or crosslinked to each other. This lack of crosslinking of the polymeric chain allows the thermoplastic polymers to be melted when subjected to high temperatures. In addition, thermoplastics are thermoformed in a reversible way, which means that they can be melted, formed into a desired structure and melted entirely, or in part, later. The ability to re-melt thermoplastics allows optional downstream processing (eg recycling) of articles generated from thermoplastics. Such TPU-based articles can also be fused in different locations, by applying a heat source to a specific location in an article. In this regard, articles generated from the disclosed TPU composition are capable of joining with the use of welding (for example, laser welding) to effectively attach the TPU-based sieving members to the appropriate sieving frames. .
[0046] The revealed TPU materials exhibit desirable properties under extreme temperature conditions and aggressive chemical environments. In exemplary embodiments, such TPU materials can be produced from a low-grade, free isocyanate monomer prepolymer (LF). An exemplary prepolymer (LF) can include a p-phenylene diisocyanate (PPDI), with a low content of free isocyanate. In other embodiments, suitable different prepolymers can be used.
[0047] Exemplary TPU materials can be generated as follows. The TPU polymer can be produced by reacting a pre
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15/35 urethane polymer, which has a free polyisocyanate monomer content of less than 1% by weight, with a curing agent. The resulting material can then be thermally processed by extrusion, at temperatures of 150 ° C (or more), to form the TPU material. The urethane prepolymer can be prepared from a polyisocyanate monomer and a polyol that includes an alkane diol, a polyether polyol, a polyester polyol, a polycaprolactone polyol and / or polycarbonate polyol. The curing agent can include a diol, a triol, a tetrol, an alkylene polyol, a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a diamine or a diamine derivative.
[0048] The revealed TPU materials can then be combined with a heat stabilizer, a flow agent and a reinforcing material, according to various modalities. In additional embodiments, other additives can be included as needed.
[0049] In general, the disclosed embodiments provide TPU compositions that can be formed by reacting a polyol with a polyisocyanate and a polymer chain extender. Exemplary embodiments include synthetic production methods and processes for producing TPU compositions. The methods disclosed may include reacting monomers, curing agents and chain extenders in a reaction vessel to form prepolymers. The disclosed methods may additionally include the formation of prepolymers by reacting a diisocyanate (OCN-R-NCO) with a diol (HO-R-OH). The formation of a prepolymer includes the chemical bonding of two reagent molecules to produce a chemical that has an alcohol (OH) in one position and an isocyanate (NCO) in another position of the product molecule. In one embodiment, a disclosed prepolymer includes both a reactive alcohol (OH) and a reactive isocyanate (NCO). The articles generated using the TPU compositions disclosed in this document can be fully cured polymeric resins that can be stored as a solid plastic.
[0050] The disclosed modalities provide prepolymers that can be prepared from a polyisocyanate monomer and a curing agent. The
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Examples without limitation of curing agents may include ethane diol, propane diol, butane diol, cyclohexane dimethanol, hydroquinone-bis-hydroxyalkyl (e.g., hydroquinone-bis-hydroxyethyl ether), diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, etc., mixture of dimethylthio-2,4-toluenediamine, di-p-aminobenzoate, phenyldiethanolamine, methylene sodium chloride dianiline complex, etc.
[0051] In exemplary embodiments, a polyol may include an alkane diol, polyether polyol, polyester polyol, polycaprolactone polyol and / or polycarbonate polyol. In certain embodiments, the polyol may include a polyol polycarbonate, alone or in combination with other polyols.
HEAT STABILIZERS
[0052] The heat / thermal stabilizers disclosed may include additives, such as organo-sulfur compounds, which are efficient hydroperoxide decomposers, which thermally stabilize the polymers. Examples without limitation of heat stabilizers include: organophosphites, such as triphenyl phosphite, tris- (2,6-dimethylphenyl) phosphite, tris- phosphite (mixed mono and di-nonylphenyl), etc .; phosphonates, such as dimethylbenzene phosphonate, etc .; phosphates, such as trimethyl phosphate, etc .; dihexylthiodiformate dicyclohexyl-1 0.1 0'-thiodidecylate dicerothyliodioformate dicerotyl-10,10'-thiodidecylate dioctyl-4,4-thiodibutyrate diphenyl-2,2'tiodiacetate (tiodiglycolate) dilauryl-3, Distearyl 3'-thiodipropionate-3,3'-thiodopropionate di- (p-tolyl) -4,4'-thiodibutyrate lauryl myristyl-3,3'-thiodipropionate palmityl stearyl-2,2'tiodiacetate dilauryl-2-methyl-2 , 2'-thiodiacetatododecyl 3- (dodecyloxycarbonylmethylthio) stearyl 4- (myristyloxycarbonylmethylthio) butyrate diheptyl-4,4-thiodibenzoate dicyclohexyl-4,4'-thiodicyclohexanoate dilauryl-5,5'-thio-4- 4- methylbenzoate; and their mixtures, etc. When present, thermal stabilizers can be included in amounts from about 0.0001% to about 5% by weight, based on the weight of the base polymer component used in the TPU composition. The inclusion of organo-sulfur compounds can also improve the thermal stability of TPU compositions, as well as the articles produced from them.
[0053] In an exemplary embodiment, a heat stabilizer can be a sterically hindered phenolic antioxidant, such as Tetrakis (3- (3,5-di-tert
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17/35 butyl-4-hydroxyphenyl) propionate) of pentaerythritol (CAS Registry 6683-19-8). In exemplary embodiments, the heat stabilizer can be included in amounts ranging from about 0.1% to about 5% by weight of the TPU.
FLOW AGENTS
[0054] Flow agents are used to enhance the flow characteristics of TPU materials, so that these TPU materials can be easily injected into a mold. The injection times for the disclosed TPU materials are preferably between about 1 and about 2 seconds. In one mode, flow times were achieved, on average, 1.6 seconds. Flow agents are used to achieve such injection times.
[0055] The disclosed TPU compositions may include flow agents that improve lubrication to increase the flow of molten polymer compositions, relative to an external surface (i.e., to increase the external flow). Flow agents can also increase the flow of individual polymer chains within a molten thermoplastic (i.e., to increase internal flow).
[0056] The disclosed embodiments provide TPU compositions that can include an internal flow agent that can be readily compatible with the polymer matrix. For example, the internal flow agent may have a similar polarity, which improves the flowability of the melt, by preventing internal friction between the individual particles of the polymer. In certain embodiments, TPU compositions, which include internal flow agents, can improve the molding characteristics. For example, in a specific embodiment, TPU compositions can be used to produce articles that have small or very small openings. In another embodiment, TPU compositions can be used to produce articles that have very fine openings by means of injection molding. In additional embodiments, the improved flow of the TPU compositions allows the production of high-resolution articles that have small or very small openings.
[0057] The revealed modalities provide TPU compositions that can
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18/35 include an external flow agent that may be more or less compatible with the polymer matrix of a TPU composition. For example, an external flow agent may have a different polarity, compared to the TPU composition polymer. Since the external flow agents may not be compatible with the TPU polymer matrix of the composition, the external flow agents may act as an external lubricating film between the polymer and the hot metal surfaces of the processing machines. In this way, external lubricants can prevent a molten polymer from sticking to parts of the machine (for example, like an extruder) and can also reduce the force required to remove a cured polymer from a mold (i.e., it can improve demoulding) in the injection molding case.
[0058] Examples without limitation of flow agents that can be included in the TPU compositions include amines (e.g., ethylene bisstearamide), waxes, lubricants, talc and dispersants. The disclosed embodiments provide TPU compositions that may also include one or more inorganic fluxing agents, such as hydrated silicas, amorphous alumina, vitreous silicas, vitreous phosphates, vitreous borates, vitreous oxides, titania, talc, mica, smoke silicas, kaolin, atapulgite , calcium silicates, alumina and magnesium silicates. The amount of flow agent may vary with the nature and particle size of the specific flow agent selected.
[0059] In exemplary embodiments, the flow agent can be a wax, such as an ethylene wax. An ethylene ester wax may include octadecanamide, N, N'-1,2-ethanedi-ylbis (C38 H76 N2 02; CAS No. 100-30-5) and stearic acid [CH3 (CH2) 16 COOH; CAS Registry No. 57-11-4], In exemplary embodiments, the flow agent can be present in amounts from about 0.1% to about 5% by weight of the TPU.
[0060] The improved flow characteristics of TPU compositions can be achieved by reducing or eliminating the presence of certain compounds, such as calcium stearate, for example.
FILLINGS
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19/35
[0061] As described above, the disclosed embodiments provide TPU compositions that may also include reinforcement, which may include inorganic materials. The reinforcements strengthen and stiffen the TPU-based material, intensifying the properties of injection-molded objects from the TPU material. For example, reinforcements help to keep the shapes of openings, holes or small pores, formed in injection molded objects, from the composition of TPU. In some embodiments, for example, fibers allow the transmission of light for use in laser welding of molded TPU components to support structures.
[0062] In exemplary embodiments, glass fibers can be used as reinforcement material, as described above. Glass fibers can take the form of solid or hollow glass tubes. In exemplary embodiments, glass tubes can have a diameter (or width, if not rounded) between about 2 pm and about 20 pm. In an exemplary embodiment, the glass fibers can have a diameter (or width, if not rounded), between about 9 pm and about 13 pm. In one embodiment, the glass fibers can have a diameter or width of 11 pm. The glass fibers can have an initial length between about 3.0 mm and 3.4 mm. In an exemplary embodiment, the glass fibers can have an initial length of 3,175 mm (ie, 1/8 inch). During the processing of the TPU material, however, the glass fibers can break and thus become shorter. In a hardened state, after injection molding, the glass fibers can have an average length of less than about 1.5 mm, with a range of most fibers being between about 1.0 mm and 3.2 mm . Some fibers retain their original length, but most break into smaller pieces.
[0063] To allow laser welding of the TPU composition, it is desirable to use as little glass fiber as possible. Excessive glass fiber leads to an unacceptably high amount of reflection / refraction of the laser light. In addition, the desired properties of the TPU composition can degrade with an increase in glass fiber content. Glass fibers that have a
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20/35 large enough diameter can work best for laser weldable compositions. Such large diameter fibers can also provide desirable strength and stiffness properties. The diameter of the glass fibers should not be excessively large, however, since the desirable flow properties can degrade with an increase in the diameter of the glass fibers, which reduces the ability of the resulting composition to suit injection molding.
[0064] Fiberglass reinforcement materials should not contain fibers that have a diameter greater than 50 pm and, preferably, should have a diameter less than 20 pm, in compositions developed for injection molding of structures that have resources in a submillimetric scale. Carbon fibers should be avoided as they may not work for laser welding because they are not translucent. TPU-based objects that are designed to be joined by laser welding can have optical properties that allow laser light to pass through the TPU material. As such, laser light can pass through the TPU object and reach adjacent structures, such as a nylon subgrade. The subgrade's nylon material is a thermoplastic that has a dark color that absorbs the laser light and can therefore be heated by the laser. By absorbing the laser light, the TPU and the adjacent nylon can be heated to a temperature above their respective melting temperatures. In this way, both materials can be melted and, after cooling, a mechanical bond can be formed at an interface between the TPU and the nylon, thereby welding the components together.
[0065] The disclosed modalities provide TPU compositions that can also include particle reinforcements, which can have any configuration, which includes, for example, spheres, plates, fibers, acicular structures (i.e., as needles), flakes, whiskers or irregular shapes. Suitable reinforcements can have a longer average dimension, in a range from about 1 nm to about 500 pm. Some embodiments may include reinforcement materials with a longer average dimension in a range from about 10 nm to about 100 pm. Some
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21/35 Fibrous, acicular or whisker-shaped reinforcement (for example, glass or wollastonite) can have an average aspect ratio (ie length / diameter) in a range of about 1.5 to about 1,000. Longer fibers can also be used in other modalities.
[0066] Reinforcement materials of the plate type (for example, mica, talc or kaolin) can have an average aspect ratio (ie average diameter of a circle of the same area / average thickness) that is greater than about 5 In one embodiment, plate-like filter materials can have an aspect ratio in the range of about 10 to about 1,000. In an additional embodiment, these plate-like materials can have an aspect ratio in the range of about 10 to about 200. Bimodal, trimodal or higher mixtures of aspect ratios can also be used. Reinforcement combinations can also be used in certain modalities.
[0067] According to one embodiment, a TPU composition can include natural, synthetic, mineral or non-mineral reinforcing materials. Suitable reinforcement materials can be chosen to have sufficient thermal resistance, so that a solid physical structure of the reinforcement can be maintained, at least at the processing temperature of the TPU composition with which it is combined. In certain embodiments, suitable reinforcements may include clays, nano-clays, carbon black, wood flour (with or without oil) and various forms of silica. Silica materials can be precipitated or hydrated, fumigated or pyrogenic, glassy, fused or colloidal. Such silica materials can include sand, glass, metals and common inorganic oxides. Inorganic oxides can include metal oxides in periods 2, 3, 4, 5 and 6 of groups IB, IIB, IIIA, IIIB, IVA, IVB (except carbon), VA, VIA, VIIA and VIII, of the periodic table.
[0068] Reinforcement materials can also include metal oxides such as aluminum oxide, titanium oxide, zirconium oxide, titanium dioxide, nanoscale titanium oxide, aluminum trihydrate, vanadium oxide, magnesium oxide , antimony trioxide, aluminum, ammonium or magnesium hydroxides. Reinforcement materials may additionally include alkali metal carbonates and
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22/35 alkaline earth, such as calcium carbonate, barium carbonate and magnesium carbonate. Mineral-based materials can include calcium silicate, diatomaceous earth, fuller earth, kieselguhr, mica, talc, slate flour, volcanic ash, cotton flake, asbestos and kaolin.
[0069] Reinforcement materials may additionally include alkali and alkaline earth metal sulphates, for example, barium sulphates and calcium sulphate, titanium, zeolites, wollastonite, titanium boride, zinc borate, tungsten carbide, ferrites, disulfide molybdenum, cristobalite, aluminosilicates including vermiculite, bentonite, montmorillonite, Na-montmorillonite, Camontmorillonite, sodium magnesium aluminum hydroxide hydroxide, pyrophyllite, magnesium and aluminum silicates, aluminum and lithium silicates, zirconium silicate compounds reinforcement described above.
[0070] The disclosed modalities provide TPU compositions that may include fibrous reinforcements, such as glass fibers (as described above), basalt fibers, aramid fibers, carbon fibers, carbon nanofibers, carbon nanotubes, carbon footballs , ultra-high molecular weight polyethylene fibers, melamine fibers, polyamide fibers, cellulose fiber, metal fibers, potassium titanate whiskers and aluminum borate whiskers.
[0071] In certain embodiments, the TPU compositions may include glass fiber reinforcement, as described above. The fiberglass reinforcements can be E glass, S glass, AR glass, T glass, D glass and R glass. In certain embodiments, the diameter of the fiberglass can be within a range of about 5 pm to about 35 pm. In other embodiments, the diameter of the glass fibers can be in the range of about 9 to about 20 pm. In additional embodiments, the glass fibers can be about 3.2 mm or less in length. As described above, TPU compositions that include glass reinforcement can impart improved thermal stability to the TPU compositions and the articles produced by them.
[0072] The disclosed modalities may include compositions that contain glass reinforcement, with concentrations in a range of about 0.1% to about 7%
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23/35 by weight. The modalities can also include glass reinforcement in concentrations ranging from about 1% to about 2%; about 2% to about 3%; 3% to about 4%; about 4% to about 5%; about 5% to about 6%; about 6% to about 7%; about 7% to about 8%; about 8% to about 9%; about 9% to about 10%; about 10% to about 11%; about 11% to about 12%; about 12% to about 13%; about 13% to about 14%; about 14% to about 15%; about 15% to about 16%; about 16% to about 17%; about 17% to about 18%; about 18% to about 19%; and about 19% to about 20%. In certain embodiments, a glass reinforcement concentration can be about 1%. In certain embodiments, a glass reinforcement concentration can be about 3%. In certain embodiments, a glass reinforcement concentration can be about 5%. In certain embodiments, a glass reinforcement concentration can be about 7%. In certain embodiments, a glass reinforcement concentration can be about 10%.
[0073] As described above, the modalities can include glass reinforcing material, wherein the individual glass fibers can have a diameter or width in a range from about 1 pm to about 50 pm. In certain embodiments, the glass reinforcement can be characterized by a narrow distribution of fiber diameters, so that at least 90% of the glass fibers have a specific diameter or width. Other modalities may include glass reinforcement that has a wider distribution of diameters or width, covering a range from about 1 pm to about 20 pm. Additional embodiments may include glass reinforcement that has a fiberglass diameter or width distribution spanning a range: from about 1 pm to about 2 pm; from about 2 pm to about 3 pm; from about 3 pm to about 4 pm; from about 4 pm to about 5 pm; from about 5 pm to about 6 pm; from about 6 pm to about 7 pm; from about 7 pm to about 8 pm; from about 8 pm to about 9 pm; from about 9 pm to about 10 pm; from about 10 pm to about 11 pm; from about 11 pm to about 12 pm; from about 12 pm to about 13 pm; from about 13 pm to about 14 pm; from about 14 pm to about 15 pm; from about 15 pm to about 16 pm; of fence
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24/35 from 16 pm to about 17 pm; from about 17 pm to about 18 pm; from about 18 pm to about 19 pm; and from about 19 pm to about 20 pm. In certain embodiments, the glass reinforcement may have a diameter or width distribution centered around a specific value. For example, the specific diameter or width value can be 10 pm ± 2 pm, according to one modality.
[0074] TPU compositions can include glass fiber reinforcements that include a surface treatment agent and, optionally, a coupling agent, according to one embodiment. Many suitable materials can be used as a coupling agent. Examples include silane-based coupling agents, titanate-based coupling agents or a mixture thereof. Applicable silane-based coupling agents, for example, can include aminosilane, epoxysilane, amidessilane, azidessilane and acrylsilane.
[0075] The disclosed modalities provide TPU compositions that can also include other suitable inorganic fibers, such as: carbon fibers, hybrid carbon / glass fibers, boron fibers, graphite fibers, etc. Various ceramic fibers can also be used, such as alumina-silica fibers, alumina fibers, silicon carbide fibers, etc. Metallic fibers, such as aluminum fibers, nickel fibers, steel, stainless steel fibers, etc., can also be used.
[0076] The disclosed TPU compositions can be generated by a process in which the TPU reagents can be combined with reinforcement materials (for example, fiber reinforcements) and other optional additives. The combination of materials can then be physically mixed in a mixing or mixing apparatus.
[0077] An example of a mixing or mixing apparatus may include: a Banbury type mixer, a twin screw extruder, a Buss Kneader type mixer, etc. In certain embodiments, the filler and base TPU composition materials can be mixed or blended to generate a TPU composition mixture that has fibers incorporated into it. The resulting TPU composition with reinforcements (for example, glass fibers) and, optionally, other
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Additional 25/35 additives, can be cooled to generate a solid mass. The resulting solid mass can then be pelleted or otherwise divided into particles of suitable size (for example, granules) for use in an injection molding process. The injection molding process can be used to generate a manufacturing article, such as a screen or screening element.
[0078] Optional additives for TPU compositions, mentioned above, can include dispersants. In certain embodiments, dispersants can help to generate a uniform dispersion of the base TPU composition and additional components, such as reinforcements. In certain embodiments, a dispersant can also improve the mechanical and optical properties of a resulting TPU composition that includes reinforcements.
[0079] In certain embodiments, waxes can be used as dispersants. Examples without limitation of wax dispersants, suitable for use in disclosed TPU compositions, include: polyethylene waxes, amide waxes and montane waxes. The TPU compositions disclosed herein may include an amide wax dispersant, such as Ν, Ν-bis-stearyl ethylenediamine. The use of such a wax dispersant may increase the thermal stability of the TPU composition, but may have little impact on the transparency of the polymer. As such, the inclusion of dispersants in the disclosed TPU compositions can have at least desirable effects: (1) improved thermal stability of compositions and articles produced therefrom and (2) desirable optical properties that are suitable for downstream processing, which includes laser welding.
[0080] The disclosed TPU compositions may additionally include antioxidants, according to a modality. Antioxidants can be used to end oxidation reactions, which can occur due to various climatic conditions and / or can be used to reduce the degradation of a TPU composition. For example, articles formed from synthetic polymers can react with atmospheric oxygen when put into service. In addition, articles formed by synthetic polymers may undergo auto-oxidation due to chain reactions
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26/35 free radicals. Oxygen sources (for example, atmospheric oxygen, alone or in combination with a free radical initiator) can react with substrates included in the disclosed TPU compositions. Such reactions can compromise the integrity of the TPU composition and the articles produced from it. The inclusion of antioxidants, for this reason, can improve the chemical stability of TPU compositions, as well as improve the chemical stability of articles generated from them.
[0081] Polymers may undergo disintegration in response to the absorption of UV light, which causes self-oxidation initiated by radicals. This auto-oxidation can lead to the dividing of hydroperoxides and carbonyl compounds. TPU compositions of the modality may include hydrogen-donating antioxidants (HA), such as hindered phenols and secondary aromatic amines. Such AH additives can inhibit the oxidation of TPU compositions through competition with organic substrates for peroxy radicals. This competition for peroxy radicals can cause chain reactions and thereby stabilize or prevent further oxidation reactions. The inclusion of antioxidants in the disclosed TPU compositions can inhibit the formation of free radicals. In addition to AH being a light stabilizer, AH can also provide thermal stability when included in the disclosed TPU compositions. Therefore, certain embodiments can include additives (for example, HA) that improve the stability of polymers exposed to UV light and heat. Articles generated from revealed TPU compositions that have antioxidants may, for that reason, be resistant to disintegration and have an improved function and / or life span when implanted under high temperature conditions, compared to articles generated from TPU compositions without antioxidants.
[0082] The disclosed TPU compositions may additionally include UV absorbers, according to one embodiment. UV absorbers convert the absorbed UV radiation into heat through reversible intramolecular proton transfer reactions. In some embodiments, UV absorbers can absorb UV radiation that would otherwise be absorbed by
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27/35 TPU composition. The resulting reduced absorption of UV rays by the TPU composition can help to reduce UV-induced disintegration of the TPU composition. Examples without limitation of UV absorbers may include oxanilides for polyamides, benzophenones for polyvinyl chloride (PVC) and benzotriazoles and hydroxyphenyltriazines for polycarbonate materials. In one embodiment, 2- (2'-hydroxy-3'-sec-butyl-5'-tert-butylphenyl) benzotriazole can provide UV light stabilization for polycarbonate, polyester, polyacetal, polyamides, TPU materials, homopolymers based of styrene and copolymers. These and other UV absorbers can improve the stability of the disclosed TPU compositions and articles produced therefrom, according to various modalities.
[0083] TPU compositions may additionally include antiozonants, which can prevent or delay the degradation of TPU materials caused by ozone gas in the air (ie, it can reduce ozone breakdown). Exemplary modalities without limiting antiozonates may include: p-phenylenediamines, such as 6PPP (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine) or IPPD (N-isopropyl-N'phenyl-p-phenylenediamine ); 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, (ETMQ) ethylene diurea (EDU) and paraffin waxes that can form a surface barrier. These and other anti-zonants can improve the stability of the disclosed TPU compositions, as well as the articles produced from them, according to various modalities.
[0084] According to one embodiment, an exemplary mixture can be prepared as follows. The starting material can be chosen to be a thermoplastic polyurethane based on polycarbonate. A reinforcement material can be chosen to have small diameter glass fibers (as described above) included in an amount between about 3% and about 10% by weight. A flow agent can then be chosen to be included in an amount between about 0.1% and about 5% by weight. In this example, the flow agent can be obtained to be a mixture of octadecanamide, N, N'-1,2-ethanedi-ylbis and stearic acid. A thermal stabilizing agent can be chosen to be pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) included in
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28/35 an amount between about 0.1% and about 5% by weight. The thermoplastic mixture described above can then be injected into bulk thermoplastic rods and then pelletized for injection molding downstream.
METHODS
[0085] The disclosed modalities provide methods and processes for generating TPU compositions. The methods disclosed may include reacting (ie, bonding) prepolymer units, which includes an alcohol (OH) and an isocyanate (NCO) to "develop" effectively and / or extend a major chain or structure of polymer. For example, in one embodiment, a TPU composition can be prepared by reacting a polyurethane prepolymer and a curing agent, usually at temperatures of about 50 ° C to about 150 ° C, for example, or from about 50 ° C to about 100 ° C. Temperatures outside these ranges can also be used in certain modalities.
[0086] The disclosed TPU compositions can be fused and formed into a desired shape, for example, by means of injection molding. The disclosed methods may additionally include a post-curing step that includes heating the TPU material to temperatures from about 50 ° C to about 200 ° C, or from about 100 ° C to about 150 ° C, for example a predetermined period of time. For example, TPU materials can be heated for about 1 hour to about 24 hours. Alternatively, various methods can include an extrusion step in which a post-cured TPU composition can be extruded at temperatures of about 150 ° C to about 270 ° C, or about 190 ° C or higher, so that the TPU composition if it takes an intermediate form. The intermediate form may be suitable for downstream processing to generate a final form, such as a TPU-based screening element.
[0087] The disclosed methods may include a variety of additional processing operations. For example, a method or process disclosed may include: promoting the reaction of a polyurethane prepolymer and a curing agent (i.e., polymerization); post-cure polyurethane; optionally grinding the material to generate a post-cured polyurethane polymer in granular form; extrude the
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29/35 post-cured and / or optionally granulated polyurethane polymer; and, optionally, pelletize the extruded TPU.
[0088] In one embodiment, the TPU composition can be generated by a process in which a prepolymer is mixed with a curing agent at temperatures of about 50 ° C to about 150 ° C to form a polymer. The method can then include heating the polymer to temperatures from about 50 ° C to about 200 ° C, for about 1 to about 24 hours, to obtain a post-cured polymer. The post-cured polymer can then be optionally milled to generate a granulated polymer. Optionally, the method may additionally include processing the post-cured polymer or the granulated polymer in an extruder, at temperatures of about 150 ° C or more, to produce a TPU composition. Additional operations can optionally include pelletizing the TPU composition, re-melting the pelletized TPU composition and extruding the fused TPU composition.
[0089] The disclosed methods may additionally include the generation of TPU compositions that contain optional additives. In one embodiment, optional additives may include antioxidants (which include phenolics, phosphites, thioesters and / or amines), antiozonants, thermal stabilizers, inert reinforcements, lubricants, inhibitors, hydrolysis stabilizers, light stabilizers, hindered amine light stabilizers, UV absorbers (eg benzotriazoles), heat stabilizers, stabilizers to prevent discoloration, dyes, pigments, inorganic and organic reinforcements, organo-sulfur compounds, thermal stabilizers, reinforcing agents and combinations thereof.
[0090] The disclosed methods include generating TPU compositions that contain optional additives in usual effective amounts for each respective additive. In various embodiments, such optional additional additives can be incorporated into the components or the reaction mixture for the preparation of the TPU composition. In other embodiments, a base TPU composition without optional additives can be generated and optionally processed. Optional processing operations can include crushing TPU materials to generate a
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30/35 granular material or form a powder-based TPU composition material, to which optional additives can be mixed, prior to further processing.
[0091] In other embodiments, powder mixtures, which include a base TPU composition and optional additives, can be mixed, melted and extruded to form a composition. In other embodiments, the TPU composition can be prepared through a reactive extrusion process, in which an extruder is directly fed with the prepolymer, curing agent and any optional additives and then which are mixed, reacted and extruded at an elevated temperature. Various alternative combinations of these formulation operations can also be used in several modalities. MANUFACTURING ITEMS
[0092] The revealed modalities include devices, articles of manufacture and products generated using TPU compositions. Exemplary embodiments without limitation may include coatings or adhesives and / or articles that have a predetermined three-dimensional structure upon curing, after being cast or extruded into a mold. The disclosed embodiments provide TPU compositions that can exhibit significantly higher load-bearing properties than other materials based on natural and synthetic rubber, for example.
[0093] In various modalities, articles generated from revealed TPU compositions can be thermostable. In this regard, although thermoplastics can generally be re-melted and reformed, articles produced from the disclosed TPU compositions may exhibit resistance to the effects resulting from thermal deformation at temperatures sufficiently lower than the melting temperature. For example, articles generated from revealed TPU compositions can maintain their shape (that is, they can exhibit module retention) at elevated temperatures corresponding to service conditions, which include temperatures in the range of about 170 ° C to about 200 ° C. The revealed TPU compositions can be used to form articles that can retain their structure, mechanical strength and general temperature performance
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31/35 high.
[0094] The disclosed TPU compositions can exhibit thermal stability in a temperature range of about 160 ° C to about 210 ° C. TPU compositions of the modality can also exhibit thermal stability for temperatures in the range of about 170 ° C to about 200 ° C, while other modalities can exhibit thermal stability for temperatures in the range of about 175 ° C to about 195 ° C. The disclosed modalities can also provide a TPU composition that can exhibit thermal stability at temperatures close to 180 ° C.
[0095] The disclosed modalities include TPU compositions that have favorable mechanical properties, characterized by cut / tear / abrasion resistance data, in relation to known thermoplastic compositions. In certain embodiments, the improved properties may include: greater resistance to tearing, better retention of the module at high temperature, low compression set, improved retention of physical properties, over time and after exposure to hazardous environments. Certain modalities provide TPU compositions that may have a combination of improved characteristics, such as superior thermal stability, abrasion resistance and chemical resistance (for example, oils and greases). In certain embodiments, articles generated from revealed TPU compositions may have highly desirable characteristics for the oil, gas, chemical, mining, automotive and other industries.
[0096] In an exemplary embodiment, an example of TPU composition, supplied in the form of pellets, can be loaded into a cylinder of an injection press. Once loaded in the cylinder, the pellet can be heated for a period of time to be melted, thereby the material of the TPU composition. The injection press can then extrude the exemplary TPU composition material melted into a mold cavity, according to a predetermined injection rate. The injection press can be adapted to include specialized tips and / or nozzles configured to reach the injection outlet
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32/35 desired.
[0097] Various parameters can be controlled or adjusted to achieve the desired results. Such parameters may include, but are not limited to, barrel temperature, nozzle temperature, mold temperature, injection pressure, injection speed, injection time, cooling temperature and cooling time.
[0098] In a method of the modality, the barrel temperatures of an injection molding apparatus can be chosen to vary from about 148 ° C to about 260 ° C, from about 176 ° C to about 233 ° C , from about 204 ° C to about 233 ° C, from about 210 ° C to about 227 ° C, and from about 215 ° C to about 235 ° C. The nozzle temperature of an injection molding apparatus can be chosen to vary from about 204 ° C to about 260 ⁰ C to about 218 ⁰ C to about 246 ⁰ C to about 234 ⁰ C to about 238 ⁰ C and about 229 ° C to about 235 ° C.
[0099] In the incorporation method, the injection pressure of an injection molding apparatus can be chosen to vary from about 2.8 MPa (400 PSI) to about 6.2 MPa (900 PSI), from about 3.4 MPa (500 PSI) at about 4.8 MPa (700 PSI), from about 4.1 MPa (600 PSI) to about 4.8 MPa (700 PSI) and about 4.3 MPa (620 PSI) at about 4.7 MPa (675 PSI). The injection speed of an injection molding apparatus can be chosen to vary from about 16.39 cubic centimeters / second (1.0 cubic inch / second) to about 49.16 cubic centimeters / second (3.0 cubic inches) / second), about 24.58 to 40.97 cubic centimeters / second (1.5 to 2.5 cubic inches / second), about 26.8 cubic centimeters / second (1.75 cubic inches / second) to about 32.77 cubic centimeters / second (2 cubic inches / second) and about 34.41 cubic centimeters / second (2.1 cubic inches / second) to about 30.33 cubic centimeters / second (2.4 inches cubic / second).
[0100] In a method of the modality, the injection time can be chosen to vary from about 0.25 seconds to about 3.00 seconds, from about 0.50 seconds to about 2.50 seconds, from about 0.75 seconds to about 2.00
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33/35 seconds and from about 1.00 seconds to about 1.80 seconds. In addition, the injection time can be modified to include a wait for a certain period of time during which the injection is paused. Waiting periods can be at any specific time. In an exemplary mode, the waiting time can vary from 0.10 seconds to 10.0 minutes. Other waiting times can be used in other ways.
[0101] In a method of the embodiment, mold temperatures can be chosen to vary from about 37 ° C to about 94 ° C, from about 43 ° C to about 66 ° C and about 49 ° C at about 60 ° C. Cooling temperatures can be gradually reduced to control the curing of a revealed TPU composition. The temperature can be gradually reduced from the mold temperature to room temperature over a period of time. The time period for cooling can be chosen to be virtually any time period ranging from seconds to hours. In one embodiment, the cooling time period can vary from about 0.1 to about 10 minutes.
[0102] The following method describes an injection molding process that generates sieving members based on the revealed TPU compositions. As described above, TPU compositions can be formed as TPU pellets. The TPU composition material can be injected first into a mold that is designed to generate a sieving member. The TPU composition can then be heated to a temperature suitable for injection molding to thereby melt the TPU material. The molten TPU material can then be loaded onto an injection molding machine. In one embodiment, the mold may be a two-cavity sieve member mold. The mold containing the injected molten TPU material can then be allowed to cool. After cooling, the TPU material solidifies into a sieve member shape defined by the mold. The resulting sieving members can then be removed from the mold for further processing.
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DEVELOPMENT OF SUITABLE COMPOSITIONS
[0103] The modalities described above provide TPU compositions expressed in bands of the various components. The improved materials were obtained by varying the composition of the TPU materials and the percentages of reinforcements, flow agents and other additives. The screening members were generated using injection molding processes based on the various compositions. The screening members were attached to the subgrade structures and mounted on large area screening assemblies that were used in field test applications.
[0104] Figure 4 illustrates an exemplary sieving assembly that was generated from sieving members and subgrade structures, as described above, with reference to Figures 1 to 3A, according to the revealed modalities.
[0105] Figure 5 illustrates results of actual field tests of screening assemblies, according to one modality. The data presented in Figure 5 represent results of test screening assemblies for screening materials produced during oil and gas exploration, at depths that extend at least about 30 km ± 2 km (100,000 feet ± 5,000 feet). The best performing composition BB had a glass fiber content (10 pm in diameter) of about 7%, while the next best performing composition BA had a glass fiber content (10 pm in diameter) of about 5%. %. Each composition also had a flow agent content of about 0.5% and a heat stabilizer content of about 1.5%. The surface elements of the sieving element 84 (for example, see Figure 2) had a thickness of about 356 pm (0.014 inches) in all tests, for which the results are shown in Figure 5.
[0106] In additional modalities, sieving members that have surface elements 84 with smaller thicknesses, which include T = 178 pm (0.007 inches), 127 pm (0.005 inches) and 7,620 pm (0.03 inches), when generated . For these modalities, it was advantageous to use lower concentrations of
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35/35 reinforcement, flow agent and thermal stabilizers, as shown in the table below.
Τ = 356 pm (0.014 inches) Τ = 178 pm (0.007 inches) T = 127 pm (0.005 inches) Τ = 76 pm (0.003 inches) Reinforcement 7% 5% 3% 2% Heat stabilizer 1.5% 1.5% 1.13% 0.85% Flow agent 0.5% 0.5% 0.38% 0.28%
[0107] The exemplary modalities are described above. Such exemplary modalities, however, should not be interpreted as limiting. In this regard, several modifications and changes can be made in this regard, without departing from its broader spirit and scope. Therefore, the specification and drawings should be considered in an illustrative sense, rather than in a restrictive sense.

权利要求:
Claims (49)
[1]
1. Composition characterized by the fact that it comprises:
a thermoplastic polyurethane, a heat stabilizer selected to optimize the heat resistance of the composition, a flow agent selected to optimize the use of the composition in injection molding, and a reinforcement, the reinforcement comprising glass fibers, in which the glass fibers are less than about 10% by weight of thermoplastic polyurethane.
[2]
2. Composition according to claim 1, characterized by the fact that the glass fibers are less than about 7 weight percent of the thermoplastic polyurethane.
[3]
Composition according to claim 1, characterized by the fact that the glass fibers are less than about 5 weight percent of the thermoplastic polyurethane.
[4]
4. Composition according to claim 1, characterized by the fact that the glass fibers are less than about 3 weight percent of the thermoplastic polyurethane.
[5]
5. Composition according to claim 1, characterized by the fact that the thermoplastic polyurethane is produced from a low-grade free isocyanate monomer prepolymer.
[6]
6. Composition according to claim 5, characterized by the fact that the low content free isocyanate monomer prepolymer is p-phenylene diisocyanate.
[7]
7. Composition according to claim 1, characterized by the fact that the thermoplastic polyurethane is obtained by means of a process in which a thermoplastic polyurethane polymer, produced by reaction of a urethane prepolymer, which has a content of free polyisocyanate monomer of less than 1% by weight, with a curing agent, is thermally processed by extrusion, at temperatures of 150 ° C or higher.
Petition 870190109780, of 10/28/2019, p. 172/187
2/6
[8]
8. Composition according to claim 7, characterized in that the urethane prepolymer is prepared from a polyisocyanate monomer and a polyol comprising an alkane diol, polyether polyol, polyester polyol, polycaprolactone polyol and / or polycarbonate polyol, and the curing agent comprises a diol, triol, tetrol, alkylene polyol, polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, diamine or diamine derivative.
[9]
9. Composition according to claim 1, characterized in that the heat stabilizer is about 0.1 percent to about 5 percent by weight of the thermoplastic polyurethane.
[10]
10. Composition according to claim 9, characterized in that the heat stabilizer comprises a sterically hindered phenolic antioxidant.
[11]
11. Composition according to claim 10, characterized by the fact that the sterically hindered phenolic antioxidant is pentaerythritol tetrakis (3- (3,5-di-tert-butyl4-hydroxyphenyl) propionate) (CAS registry 6683-19 -8).
[12]
12. Composition according to claim 1, characterized in that the flow agent is from about 0.1 percent to about 5 percent by weight of the thermoplastic polyurethane.
[13]
13. Composition according to claim 12, characterized in that the flow agent comprises an ethylene wax.
[14]
14. Composition according to claim 13, characterized by the fact that the ethylene wax comprises octadecanamide, N, N'-1,2-ethanediilbis (CAS record 110-30-5) and stearic acid (CAS record 57 -11-4).
[15]
15. Composition according to claim 1, characterized in that the glass fibers have a diameter or width less than about 20 pm.
[16]
16. Composition according to claim 1, characterized in that the glass fibers have a diameter or width between about 9 and 13 pm.
[17]
17. Composition according to claim 1, characterized by the fact that the glass fibers have an initial length of less than about 3.4 mm.
[18]
18. Composition, according to claim 1, characterized by the fact that
Petition 870190109780, of 10/28/2019, p. 173/187
3/6 that glass fibers have an initial length between about 3.1 mm and about 3.2 mm.
[19]
19. Composition according to claim 1, characterized by the fact that the glass fibers, in a hardened state after injection molding, have an average length of less than about 1.5 mm.
[20]
20. Composition according to claim 1, characterized in that the glass fibers, in a hardened state after injection molding, have a length distribution between about 1.0 mm and about 3.2 mm .
[21]
21. Composition according to claim 1, characterized in that it additionally comprises an ultraviolet light stabilizer.
[22]
22. Composition, according to claim 1, characterized by the fact that the articles of manufacture, which are molded from the composition, are laser weldable articles.
[23]
23. Method of manufacturing a composition, suitable for use, in injection molding, of articles of manufacture that have fine pores, characterized by the fact that it comprises:
promote the reaction of a thermoplastic polyurethane, a heat stabilizer, a flow agent and a reinforcement, at a temperature above about 150 ° C, to produce a thermoplastic polyurethane composition, the reinforcement comprising glass fibers, in that glass fibers are less than about 10% by weight of thermoplastic polyurethane.
[24]
24. Composition according to claim 23, characterized in that the glass fibers are less than about 7% by weight of the thermoplastic polyurethane.
[25]
25. Composition according to claim 23, characterized in that the glass fibers are less than about 5% by weight of the thermoplastic polyurethane.
[26]
26. Composition according to claim 23, characterized in that the glass fibers are less than about 3 weight percent of the thermoplastic polyurethane.
Petition 870190109780, of 10/28/2019, p. 174/187
4/6
[27]
27. Composition according to claim 23, characterized by the fact that the thermoplastic polyurethane is produced from a low content free isocyanate monomer prepolymer.
[28]
28. Composition according to claim 27, characterized in that the low content free isocyanate monomer prepolymer is p-phenylene diisocyanate.
[29]
29. Composition according to claim 23, characterized by the fact that thermoplastic polyurethane is obtained by means of a process in which a thermoplastic polyurethane polymer, produced by reaction of a urethane prepolymer, which has a content of free polyisocyanate monomer of less than 1% by weight, with a curing agent, is thermally processed by extrusion, at temperatures of 150 ° C or more.
[30]
30. Composition according to claim 29, characterized in that the urethane prepolymer is prepared from a polyisocyanate monomer and a polyol comprising an alkane diol, polyether polyol, polyester polyol, polycaprolactone polyol and / or polycarbonate polyol, and the curing agent comprises a diol, triol, tetrol, alkylene polyol, polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, diamine or diamine derivative.
[31]
31. Composition according to claim 23, characterized in that the heat stabilizer is from about 0.1 percent to about 5 percent by weight of the thermoplastic polyurethane.
[32]
32. Composition according to claim 31, characterized in that the heat stabilizer comprises a sterically hindered phenolic antioxidant.
[33]
33. Composition according to claim 32, characterized by the fact that the sterically hindered phenolic antioxidant is pentaerythritol tetrakis (3- (3,5-di-tert-butyl4-hydroxyphenyl) propionate) (CAS registry 6683-19 -8).
[34]
34. Composition according to claim 23, characterized in that the flow agent is about 0.1 percent to about 5 percent by weight of the thermoplastic polyurethane.
Petition 870190109780, of 10/28/2019, p. 175/187
5/6
[35]
35. Composition according to claim 34, characterized in that the flow agent comprises an ethylene wax.
[36]
36. Composition according to claim 35, characterized by the fact that the ethylene wax comprises octadecanamide, N, N'-1,2-ethanediilbis (CAS Registry 110-30-5) and stearic acid (CAS Registry 57 -11-4).
[37]
37. Composition according to claim 23, characterized in that the glass fibers have a diameter or width less than about 20 pm.
[38]
38. Composition according to claim 23, characterized in that the glass fibers have a diameter or width between about 9 and about 13 pm.
[39]
39. Composition according to claim 23, characterized in that the glass fibers have an initial length of less than about 3.4 mm.
[40]
40. Composition according to claim 23, characterized by the fact that the glass fibers have an initial length between about 3.1 mm and about 3.2 mm.
[41]
41. Composition according to claim 23, characterized in that the glass fibers, in a hardened state after injection molding, have an average length of less than about 1.5 mm.
[42]
42. Composition according to claim 23, characterized in that the glass fibers, in a hardened state after injection molding, have a length distribution between about 1.0 mm and about 3.2 mm .
[43]
43. Composition according to claim 23, characterized in that it additionally comprises an ultraviolet light stabilizer.
[44]
44. Composition according to claim 23, characterized in that the articles of manufacture that are molded from the composition are laser weldable articles.
[45]
45. Method of producing a screening member for a vibrating shaker screen characterized by the fact that it comprises:
promote the reaction of a thermoplastic polyurethane, a heat stabilizer, a flow agent and a fiberglass reinforcement, at a temperature above
Petition 870190109780, of 10/28/2019, p. 176/187
6/6 about 150 ° C, to produce a thermoplastic polyurethane composition;
providing a mold for a sieving member;
introducing the thermoplastic polyurethane composition produced in the mold so that a sieving member thereby forms a sieving member; and removing the sieving member from the mold for a sieving member, wherein the sieving member has a large plurality of openings from about 38 pm to about 150 pm.
[46]
46. Method according to claim 45, characterized by the fact that the mold is an injection mold.
[47]
47. Method according to claim 45, characterized by the fact that the sieving member effectively sieves particles at temperatures up to about 38 ° C to 94 ° C.
[48]
48. Screening member for a vibrating screening machine characterized by the fact that it comprises:
a sieving injection molded from a composition, as defined in claim 1, and the sieving member having openings from about 38 pm to about 150 pm.
[49]
49. Sieving member according to claim 48, characterized in that the sieving member effectively sifts particles at temperatures up to about 37 ° C to 94 ° C.

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同族专利:

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公开号 | 公开日

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CN110691821A|2020-01-14|

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EP3615612A2|2020-03-04|

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GB2575613A|2020-01-15|

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WO2018201043A3|2019-04-11|

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MX2019012763A|2019-12-16|

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US20180312667A1|2018-11-01|

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EP3615612A4|2020-12-02|

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TW201843236A|2018-12-16|

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CO2019011855A2|2020-04-01|

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US11203678B2|2021-12-21|

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GB201916470D0|2019-12-25|

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CL2019003079A1|2020-02-07|

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WO2018201043A2|2018-11-01|

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CA3060677A1|2018-11-01|

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AU2018260541A1|2019-11-07|

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PE20200680A1|2020-06-11|

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法律状态:
2021-10-19| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2022-01-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US201762492054P| true| 2017-04-28|2017-04-28|

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US201762500262P| true| 2017-05-02|2017-05-02|

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PCT/US2018/029944|WO2018201043A2|2017-04-28|2018-04-27|Thermoplastic compositions, methods, apparatus, and uses|

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