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    • 专利摘要:
    UHMWPE FIBER WITH IMPROVED DEFORMATION The invention relates to an ultra-high molecular weight polyethylene fiber (UHMWPE) presenting improved deformation obtained by spinning a UHMWPE comprising olefinic elongation (ES) and an (OB) branches, and presenting a tension (OB / 1,000C) / ES ratio between the number of olefinic branches per thousand carbon atoms (OB / 1,000C) and the elongation stress (ES) of at least 0.2, where the UHMWPE fiber when subjected at a load of 600 MPa at a temperature of 70 ° C, it has a deformation duration of at least 90 hours.
    公开号:BR112013026052B1
    申请号:R112013026052-1
    申请日:2012-04-03
    公开日:2020-12-29
    发明作者:Jorn Boesten；Martin Pieter Vlasblom；Piotr Matloka；Timothy James Kidd；Romain BERTHOUD；Johannes Hendrikus Marie Heijnen
    申请人:Dsm Ip Assets B.V；
    IPC主号:
    专利说明:

    This invention relates to an ultra-high molecular weight polyethylene fiber (UHMWPE) with improved deformation, a process for producing the same and several products, such as ropes, nets, medical devices, fabrics, laminates, composite articles and bulletproof articles containing said UHMWPE fibers.
    During the last decades, many research projects have focused on improving the deformation properties of synthetic fibers, since such fibers are extremely suitable for a wide range of applications in which strength and low weight are paramount factors. An example of synthetic fibers are UHMWPE fibers that successfully meet the strength and weight requirements. The almost unmatched strength of UHMWPE fibers combined with ultraviolet resistance, chemical resistance, cut and abrasion resistance and other favorable properties are the reasons why these fibers find an almost immediate use in mooring ropes, composite reinforcement, medical devices, cargo nets and the like.
    UHMWPE fibers, however, have a disadvantage that acts as an impediment to their better use in long-term applications, this disadvantage is related to their deformation behavior. It has been observed that the final failure mode of a system using UHMWPE fibers and specifically those systems placed under long-term load is rupture or failure due to deformation. Such systems, and particularly those intended for long-term or ultra-long-term use, must therefore be designed to last for several years, for example, more than 10 years, and in some cases even more than 30 years. Therefore, an immediate need was felt in the industry, that is, the need for a UHMWPE fiber having an improved deformation behavior. Consequently, many research projects with the aim of improving UHMWPE fibers are focused on their deformation behavior and almost all of these projects have an exclusive focus on improving their deformation rate.
    For example, it was recognized by the inventors of JP 6280111 that fibers made from branched UHMWPE polymers can be made of fibers with good resistance to deformation. JP 6280111 thus describes a highly branched UHMWPE, for example, having more than one branch per 100 C atoms, and a method for making fibers from them. However, it has been observed that the high branching of UHMWPE, as described in JP 6280111, can have deleterious effects on the final properties of the fibers and may not yet provide a fiber with an improved deformation behavior.
    Other examples of UHMWPE fibers showing good deformation behavior and a process for producing them are known from EP 1,699,954; which discloses UHMWPE fibers with strain rates as low as 1 x 10-6 sec-1 measured at 70 ° C under a load of 600 MPa and tensile strengths as high as 4.1 GPa.
    WO 2009/043598 and WO 2009/043597 also describe UHMWPE fibers having a good combination of strain rate and tear strength, for example, a strain rate of a maximum of 5 x 10-7 sec-1 measured at 70 ° C under a load of 600 MPa, and a tensile strength of at least 4 GPa.
    US 5,578,374 discloses a UHMWPE fiber with a low deformation rate, high modulus, low shrinkage and high toughness, showing good resistance retention at high temperatures and methods for producing such fibers.
    The present inventors have observed, however, that apart from the deformation rate of UHMWPE fibers, other deformation properties have yet to be improved. Under constant load, UHMWPE fibers show an irreversible deformation that depends heavily on load and temperature. The rate of irreversible strain is called the strain rate and is a measure of how fast UHMWPE fibers undergo such deformation. However, the survivability of UHMWPE fibers under a long-term load, or in other words, the time during which UHMWPE fibers can be used for a specific application, without the need to be replaced, also needs to be improved. Very surprisingly, it has been observed that UHMWPE fibers with good deformation rates can show a somewhat weak survivability.
    Therefore, it is immediately recognized that from an engineering perspective, he said that the survival capacity of UHMWPE fibers is the property that needs to be primarily improved, as in turn, the design and / or the useful life of any system or service that uses them can also be improved. In addition, it was observed that, despite the enormous amount of research on improving the deformation rate, UHMWPE fibers that have an excellent survivability are not currently available.
    An objective of the present invention can therefore be to provide a UHMWPE fiber having an improved survivability. An additional object of the present invention may be to provide a UHMWPE fiber that has improved survivability and also good tensile properties, for example, tensile strength, modulus of elasticity and / or elongation at break. An additional objective of the present invention may be to provide a UHMWPE fiber having an improved survivability, when compared to the survivability of existing UHMWPE fibers.
    The invention provides an improved strain UHMWPE fiber obtained by spinning a UHMWPE comprising olefinic branches (OB), and having an elongation stress (ES) and a ratio of (OB / 1,000C) between the number of olefinic branches per thousand atoms carbon (OB / 1,000C) and the elongation stress (ES) of at least 0.2, where the UHMWPE fiber when subjected to a load of 600 MPa at a temperature of 70 ° C, has a deformation duration at least 90 hours, preferably at least 100 hours, more preferably at least 110 hours, even more preferably at least 120 hours, more preferably at least 125 hours. Preferably, the UHMWPE has an intrinsic (IV) viscosity of at least 5 dl / g.
    It was observed that by improving the duration of the deformation of a fiber, its ability to survive under a long-term load can also be improved. In particular, it has been observed that the UHMWPE fibers of the invention can be produced according to the invention, said fibers having a deformation duration hitherto never achieved by any existing UHMWPE fiber. It was further observed that, due to the improved deformation properties, the improved UHMWPE fiber of the invention is useful in a variety of applications and, in particular, in applications where a long or ultra-long load is applied to said fibers, for example example, in the mooring of the offshore oil production platform. Long-term load is understood herein as a load which is applied to the UHMWPE fibers of the invention for a period of at least 5 years, more preferably, at least 10 years, more preferably for at least 20 years, preferably , under normal conditions of use, for example, humidity, temperature and load. For example, for anchoring at sea, normal load conditions can be loads of a maximum of 70% of the breaking load of the fibers or the product containing said fibers, such as ropes, and the normal temperature conditions can be the temperature environment, for example, water at various depths or above water. The inventors have also observed that the design of systems or devices intended for applications of long and ultra-long duration and which comprise the UHMWPE fibers of the invention, can be less complicated and laborious.
    Preferably, the olefinic branches have a number of carbon atoms between 1 and 15, more preferably between 2 and 10, more preferably between 2 and 6. Good results were obtained when the branches were ethyl branches (C = 2) or butyl ramifications (C = 4).
    Therefore, in one embodiment, the invention provides an UHMWPE fiber of improved strain obtained by spinning a UHMWPE comprising ethyl branches and with an intrinsic viscosity (IV), preferably at least 5 dl / g, an elongation stress (ES ), and a ratio (C2H5 / 1,000C) between the number of ethyl branches per thousand carbon atoms (C2H5 / 1,000C) and the elongation stress (ES) of at least 0.5, in which said fiber UHMWPE when subjected to a load of 600 MPa at a temperature of 70 ° C, has a deformation duration of at least 90 hours, preferably at least 100 hours, more preferably at least 110 hours, even more preferably at least 120 hours, more preferably at least 125 hours.
    In another embodiment, the invention provides a UHMWPE fiber of improved strain by spinning a UHMWPE comprising butyl branches and having an intrinsic viscosity (IV), preferably at least 5 dl / g, an elongation stress (ES), and a ratio (C4H9 / 1,000C) between the number of butyl branches per thousand carbon atoms (C4H9 / 1,000C) and the elongation stress (ES) of at least 0.2, in which the said UHMWPE fiber when submitted at a load of 600 MPa, at a temperature of 70 ° C, it has a deformation duration of at least 90 hours, preferably at least 100 hours, more preferably at least 110 hours, even more preferably at least 120 hours, more preferably at least 125 hours.
    Fiber is understood in the present document as an elongated body, for example, a body with a transverse length and dimensions, where the length of the body is much greater than its transverse dimensions. The term fiber as used herein can also include various embodiments, for example, a filament, a ribbon, a strip, a ribbon and a yarn. The fiber can also have regular or irregular cross sections. The fiber can also have a continuous length and / or a discontinuous length. Preferably, the fiber has a continuous length, such a fiber being known in the art as a filament. Within the context of the invention, a yarn is understood to be an elongated body comprising a plurality of fibers.
    Preferably, the duration of the deformation of the UHMWPE fibers of the invention, as described in the embodiments described earlier in this document, is at least 150 hours, more preferably at least 200 hours, even more preferably at least 250 hours, even more preferably at least minus 290 hours, even more preferably at least 350 hours, even more preferably at least 400 hours, more preferably at least 445 hours. Such good deformation durations were particularly obtained for the modalities of fibers spun from UHMWPEs with ethyl and butyl branches. Deformation duration is measured on multiple filament yarns according to the methodology described in the measurement methods section below.
    Preferably, the UHMWPE fibers of the invention, and in particular those that are spun from UHMWPEs having branches of ethyl or butyl, are subjected to an elongation during their deformation, under a load of 600 MPa and at a temperature of 70 ° C at most 20%, more preferably at most 15%, even more preferably at most 9%, even more preferably at most 7%, yet even more preferably at most 5%, most preferably at most 3 , 7%. It was observed that UHMWPE fibers with the duration of such long deformation and low elongation have never been produced to date, in particular when these properties were subjected to high loads and high temperatures, such as those used in the present invention.
    Preferably, the UHMWPE fibers of the invention and, in particular those spun UHMWPEs having ethyl or butyl branches have a toughness of at least 25 cN / dtex, more preferably at least 32 cN / dtex, more preferably at least 38 cN / dtex. Preferably, the UHMWPE fibers of the invention and in particular those spun from UHMWPEs having ethyl or butyl branches have an elastic modulus of at least 1,100 cN / dtex, more preferably at least 1,200 cN / dtex, more preferably at least 1,300 cN / dtex. It has been observed that, in addition to the excellent sliding properties, the UHMWPE fibers of the invention also have good tensile properties.
    According to the invention, the UHMWPE fibers of the invention are obtained by a spinning process, for example, gel spinning or melt spinning. Preferably, the UHMWPE fibers of the invention and, in particular, those which have UHMWPEs spun from ethyl or butyl branches are obtained by a gel spinning process, in the art such fibers are also referred to as "spun UHMWPE fibers with gel. ”Thus, the fibers of the present invention are preferably obtained by gel spinning a UHMWPE comprising ethyl branches or butyl branches and having a number of branches per thousand carbon atoms, an ES and an IV as described throughout of this document.
    In the present invention the term gel spinning process means a process that comprises at least the steps of: (a) preparing a solution comprising a UHMWPE and a suitable solvent for the UHMWPE; (b) extruding said solution through a spinner to obtain a gel fiber containing said UHMWPE and said solvent for UHMWPE, and (c) extracting the solvent from the fiber with gel to obtain a continuous fiber. The gel spinning process can optionally also contain a stretching step in which the gel fiber and / or the continuous fiber are designed with a certain stretching rate. Gel spinning processes are known in the art and are disclosed, for example, in WO 2005/066400, WO 2005/066401, WO 2009/043598, WO 2009/043597, WO 2008/131925, WO 2009/124762, EP 0205960 A, EP 0213208 A1, US 4413110, GB 2042414 A, GB-A-2051667, EP 0200547 B1, EP 0472114 B1, WO 2001/73173 A1, EP 1,699,954 and in "Advanced Fiber Spinning
    Technology ”Ed. T. Nakajima, Woodhead Publ. Ltd (1994), ISBN 185573 182 7, these publications and the references cited in this document being included as a reference.
    According to the invention, the gel spinning process for making the UHMWPE fibers of the invention uses a UHMWPE polymer. The term UHMWPE is understood herein as a polyethylene with an intrinsic viscosity (IV) as measured in the decalin solution at 135 ° C, preferably at least 5 dl / g. Preferably, the UHMWPE IV is at least 10 dl / g, more preferably at least 15 dl / g, even more preferably at least 19 dl / g, more preferably at least 21 dl / g. More preferably, the IV is at most 40 dl / g, more preferably at most 30 dl / g, even more preferably at most 25 dl / g.
    The UHMWPE used in the present invention preferably has a ratio (OB / 1,000C) of at least 0.3, more preferably at least 0.4, even more preferably at least 0.5, even more preferably at least 0, 7, even more preferably at least 1.0 and even more preferably at least 1.2. It has surprisingly been observed that by increasing the aforementioned ratio, the properties of the UHMWPE fibers of the invention can be improved.
    When the UHMWPE used in the present invention has ethyl branches, said UHMWPE preferably has a C2H5 / 1,000C ratio of at least 1.00, ES more preferably at least 1.30, even more preferably at least 1.45 , even more preferably at least 1.50, more preferably at least 2.00. Preferably, said ratio is between 1.00 and 3.00, more preferably between 1.20 and 2.80, even more preferably between 1.40 and 1.60, even more preferably between 1.45 and 2, 20.
    When the UHMWPE used in the present invention has butyl branches, said UHMWPE preferably has a C4H9 / 1,000C ratio of at least 0.25, even more preferably at least 0.30, even more preferably at least 0.40 , even more preferably at least 0.70, more preferably at least 1.00, most preferably at least 1.20. Preferably, said ratio is between 0.20 and 3.00, more preferably between 0.40 and 2.00, even more preferably between 1.40 and 1.80.
    The UHMWPE used in the present invention preferably has an ES of a maximum of 0.70, more preferably a maximum of 0.50, more preferably a maximum of 0.49, even more preferably a maximum of 0.45, plus preferably not more than 0.40. When said UHMWPE has ethyl branches, preferably said UHMWPE has an ES between 0.30 and 0.70, more preferably between 0.35 and 0.50. When said UHMWPE has butyl branches, preferably said UHMWPE has an ES between 0.30 and 0.50, more preferably between 0.40 and 0.45.
    The UHMWPE used according to the invention preferably also has an amount of olefinic branches per thousand carbon atoms (OB / 1,000C) between 0.05 and 1.30, more preferably between 0.10 and 1.10 , even more preferably between 0.30 and 1.05.
    When the UHMWPE used in accordance with the invention has ethyl branches, preferably said UHMWPE has an amount of ethyl branches per thousand carbon atoms (C2H5 / 1,000C) between 0.40 and 1.10, more preferably between 0, 60 and 1.10. In a first preferred embodiment, C2H5 / 1,000C is between 0.63 and 0.75, preferably between 0.64 and 0.72, more preferably between 0.65 and 0.70. For the first preferred embodiment, it has been observed that the strength properties of the UHMWPE fibers of the invention have been improved while at the same time obtaining a unique strain time. In a second preferred embodiment, C2H5 / 1,000C is between 0.78 and 1.10, preferably between 0.90 and 1.08, more preferably between 1.02 and 1.07. For the second preferred embodiment, it has been observed that the duration of the deformation of the UHMWPE fibers of the invention has been improved.
    When the UHMWPE used in accordance with the invention has butyl branches, preferably said UHMWPE has an amount of butyl branches per thousand carbon atoms (C4H9 / 1,000C) between 0.05 and 0.80, more preferably between 0, 10 and 0.60, even more preferably between 0.15 and 0.55, more preferably between 0.30 and 0.55.
    In a preferred embodiment, the UHMWPE fiber of the invention is obtained by spinning with UHMWPE gel comprising ethyl branches and having an elongation tension (ES), where the ratio (C2H5 / 1,000C) between ES is the number of ethyl branches per thousand carbon atoms (C2H5 / 1,000C) and the stretching stress (ES) is at least 1.0 where C2H5 / 1,000C is between 0.60 and 0.80 and where ES is between 0.30 and 0.50. Preferably, the UHMWPE has an IV of at least 15 dl / g, more preferably at least 20 dl / g, more preferably at least 25 dl / g. Preferably, the fiber of the invention has a deformation duration of at least 90 hours, preferably at least 150 hours, more preferably at least 200 hours, even more preferably at least 250 hours and even more preferably at least 290 hours .
    In another preferred embodiment, the UHMWPE fiber of the invention is obtained by spinning with gel from a UHMWPE comprising ethyl branches and having an elongation tension (ES), where the ratio (C2H5 / 1,000C) between the number of ethyl branches per thousand carbon atoms (C2H5 / 1,000C) and the elongation stress (ES) is at least 1.0, where C2H5 / 1,000C is between 0.90 and 1.10 and where
    ES is between 0.30 and 0.50. Preferably, the UHMWPE has an IV of at least 15 dl / g, more preferably of at least 19 dl / g. Preferably, the fiber of the invention has a deformation life of at least 90 hours, preferably at least 150 hours, more preferably at least 250 hours and most preferably at least 350 hours.
    In another preferred embodiment, the UHMWPE fiber of the invention is obtained by spinning a UHMWPE gel comprising butyl branches and having an elongation tension (ES), where the ratio (C4H9 / 1,000C) between the ES number of branches of butyl per thousand carbon atoms (C4H9 / 1,000C) and the stretching tension (ES) is at least 0.5, where C4H9 / 1,000C is between 0.20 and 0.80 and where ES is between 0.30 and 0.50. Preferably, the UHMWPE has an IV of at least 15 dl / g, more preferably at least 20 dl / g. Preferably, the fiber of the invention has a deformation duration of at least 90 hours, more preferably at least 200 hours, even more preferably at least 300 hours, even more preferably at least 400 hours, most preferably at least least 500 hours.
    Preferably, any UHMWPE used according to the invention is obtained by a suspension polymerization process in the presence of an olefin polymerization catalyst at a polymerization temperature, said process comprising, in the sequence that follows, the steps of: ) loading a stainless steel reactor with: i. a non-polar aliphatic solvent having a boiling point under standard conditions, above that of the polymerization temperature, where said polymerization temperature is preferably between 50 ° C and 90 ° C, more preferably between 55 ° C and 80 ° C, more preferably between 60 ° C and 70 ° C; wherein said boiling point of said solvent is between 60 ° C and 100 ° C; wherein said solvent is preferably chosen from the group consisting of heptane, hexane, pentamethylheptane and cyclohexane; ii. an alkyl aluminum, as a cocatalyst, such as triethyl aluminum (TEA) or triisobutyl aluminum (TIBA); iii. ethylene gas at a pressure between 10 and 500 kPa.g, preferably between 100 and 300 kPa.g, more preferably between 180 and 220 kPa.g; iv. an alpha-olefinic comonomer; v. a Ziegler-Natta catalyst suitable for producing UHMWPE under conditions a) -i) a) -iv); b) a gradual increase in the pressure of ethylene gas inside the reactor, for example, by adjusting the flow of ethylene gas until it reaches a maximum ethylene gas pressure of 1,000 kPa.g, during the course of the polymerization process, and c) polymerization of UHMWPE molecules so that they produce UHMWPE particles having an average particle size (D50) as measured by ISO 13320-1, comprised between 80 μm and 300 μm, more preferably between 100 μm and 200 μm, more preferably between 140 μm and 160 μm. The alpha-olefinic comonomer is chosen taking into account the type of branch required.
    In one embodiment, in order to produce a UHMWPE with ethyl branches, the alpha-olefinic comonomer is butene gas, more preferably 1-butene gas, in a gas: total ethylene (NL: NL) ratio of at most 325: 1, preferably at most 150: 1, even more preferably at most 80: 1, where by total ethylene is meant the ethylene added in steps a) -III) and b).
    In another embodiment, in order to produce a UHMWPE with butyl, for example, n-butyl or hexyl branches, the olefinic comonomer is 1-hexene or 1-octene, respectively. Preferably, the butyl branches are understood here as n-butyl branches.
    It was observed that with the above polymerization process a UHMWPE was obtained which allowed the manufacture of UHMWPE fibers of the invention with unique deformation properties. The invention, therefore, also relates to the above polymerization process for obtaining a UHMWPE as used in the present invention and a UHMWPE obtained with said process.
    The invention additionally relates to a UHMWPE comprising olefinic branches and having an elongation stress (ES) and a ratio of (OB / 1,000C) between ES the number of olefinic branches per thousand carbon atoms (OB / 1,000C) and the stretching stress (ES) of at least 0.2. Preferably the UHMWPE IV is at least 5 dl / g. Preferably, the olefinic branches have a number of carbon atoms between 1 and 15, more preferably between 2 and 10, more preferably between 2 and 6. Good results were obtained when the branches were ethyl branches (C = 2) or butyl ramifications (C = 4). The invention also relates to the various modalities of UHWMPE as presented throughout this disclosure.
    It may be desirable in step a) of the process for making UHMWPE according to the invention, hereinafter simply referred to as "the UHMWPE manufacturing process of the invention" that the donor compound can be added to the solvent. Preferably, the donor compound can be classified as an organic molecule having Lewis basicity that can react or modify the catalyst / co-catalyst in order to increase the molecular weight capacity. One donor that can be employed is, for example, an alkoxy silane compound. More preferably, said silane compound is an alkoxy silane compound having substituents ranging from methoxy groups (OCH3) to isopropoxy groups (OCH (CH3) 2). The most preferred substituents are ethoxy groups (OCH2CH3). A suitable example of such a silane compound is tetraethyl orthosilicate (TEOS). The amount of silane compound is preferably between 0.01 and 0.2 mmol / (liter of solvent), more preferably between 0.03 and 0.1 mmol / (liter of solvent), most preferably between 0, 05 and 0.07 mmol / (liter of solvent).
    Preferably, the olefin polymerization catalyst used in the UHMWPE manufacturing process of the invention is a titanium-based Ziegler-Natta catalyst for the production of UHMWPE. Examples of suitable catalysts are described in WO 2008/058749 or EP 1 749 574 which are included herein by reference.
    Preferably, said catalyst component is in the form of particles having an average diameter of less than 20 micrometers, more preferably less than 10 micrometers, more preferably, the particle size is between 2 and 8 micrometers. Preferably, the particle size distribution characteristic for said catalyst and measured with Malvern Mastersizer equipment is at most 1.5, more preferably at most 1.3, most preferably at most 1. Most preferably said distribution particle size is between 0.5 and 0.9.
    It was observed that, when the UHMWPE obtained by the manufacturing process of the present invention is used, the UHMWPE fibers have an incomparable deformation duration. Despite not being able to explain the reasons for the improvement of the unique deformation duration, the inventors attributed the said improvement partially to the specific process obtained to obtain the said UHMWPE.
    According to the invention, a gel spinning process is used to manufacture the UHMWPE fibers of the invention, in which, as already mentioned, the UHMWPE is used to produce a UHMWPE solution which is subsequently centrifuged through a spinner and the fiber obtained with gel is dried to form a solid fiber.
    The UHMWPE solution is preferably prepared with a UHMWPE concentration of at least 3% by weight, more preferably at least 5% by weight. Preferably, the concentration is between 3 and 15% by weight for UHMWPE with an IV in the range of 15-25 dl / g.
    In order to prepare the UHMWPE solution any known solvent for spinning with UHMWPE gel can be used. Such solvents are also referred to herein as "spinning solvents". Suitable examples of solvents include aliphatic and alicyclic hydrocarbons, for example, octane, nonane, decane and paraffins, including their isomers; fractions of petroleum, mineral oil, kerosene, aromatic hydrocarbons, for example, toluene, xylene and naphthalene including hydrogenated derivatives thereof, for example, decalin and tetraline, halogenated hydrocarbons, for example, monochlorobenzene, and cycloalkanes or cycloalkenes, for example, “careen ”, Fluorine, camphene, menthane, dipentene, naphthalene, acenaphthalene, methylcyclopentandien, tricyclodecane, 1,2,4,5-tetramethyl-1,4-cyclohexadiene, fluorenone, naphthomethane, tetramethyl-p-benzodiquinone, ethylfluorene and fluoranthene and fluoranthene. Combinations of the aforementioned solvents can also be used for spinning UHMWPE with gel, the solvent combination also being referred to for simplification as a solvent. In a preferred embodiment, the solvent of choice is not volatile at room temperature, for example, paraffin oil. It has also been found that the process of the invention is especially advantageous for relatively volatile solvents at room temperature, such as, for example, decalin, tetralin and kerosene classifications. In the most preferred embodiment, the solvent of choice is decaline.
    The UHMWPE solution is then formed in gel filaments by spinning said solution through a spinner, preferably containing multiple rotation holes. The term spinner containing several rotation holes is understood herein as a spinner preferably containing at least 100, even more preferably at least 300, more preferably at least 500 rotation holes. Preferably, the spinning temperature is between 150 ° C and 250 ° C, more preferably said temperature is chosen below the boiling point of the spinning solvent. If, for example, decalin is used as the spinning solvent, the spinning temperature will preferably be at most 190 ° C.
    The gel filaments formed by spinning the UHMWPE solution through the spinneret are extruded into an air gap, and then inside a cooling zone from where they are collected in a first driven roller. Preferably, the gel filaments are stretched in the air gap. In the cooling zone, the gel filaments are preferably cooled in a gas stream and / or in a liquid bath.
    Subsequent to the formation of the gel filaments, said gel filaments are subjected to a solvent extraction step in which the spinning solvent used to manufacture the UHMWPE solution is at least partially removed from the gel filaments to form continuous filaments. The solvent removal process can be carried out by known methods, for example, by evaporation when a relatively volatile spinning solvent, for example, decalin, is used or by using an extraction liquid, for example, when paraffin is used as a spinning solvent, or by a combination of both methods. Preferably, the gel filaments are entrained with a drag rate preferably of at least 1.2, more preferably of at least 1.5, more preferably of at least 2.0.
    Preferably, the solid filaments are also entrained during and / or after the removal of said solvent. Preferably, the dragging of the solid filaments is carried out in at least one drag step with a drag rate preferably of at least 4, more preferably at least 7, even more preferably at least 10. Most preferably, the dragging of the solid filaments it is carried out in at least two stages, even more preferably in at least three stages.
    Preferably, a gel spinning process, in accordance with WO 2005/066400, WO 2005/066401, WO 2009/043598, WO 2009/043597, WO 2008/131925; WO 2009/124762 is used for the manufacture of UHMWPE fibers of the invention.
    The UHMWPE fibers of the invention have properties that make them an interesting material for use in cables, ropes and the like, preferably ropes designed for heavy load operations, such as, for example, in marine, industrial and offshore operations. The cables, devices and ropes used in sports applications, such as, in yachts, climbing, gliding, parachuting and the like are also applications where the fibers of the invention can perform well. In particular, it has been found that the UHMWPE fibers of the invention are particularly useful for long-term and ultra-long-term heavy load operations.
    Heavy load operations may also include, but are not restricted to crane pulleys for offshore deployment or hardware recovery, anchor handling, mooring support platforms for the generation of renewable energy at sea, mooring offshore platforms. oil drilling and production platforms, such as offshore production platforms and the like. It has been surprisingly observed that, for such operations, and in particular for mooring at sea, the installation of cables designed for this operation can be improved, for example, the cables can be installed using less complex equipment or smaller and lighter installation equipment .
    The UHMWPE fibers of the invention are also very suitable for use as a reinforcement element, for example, in a liner, for reinforced products, such as hoses, tubes, pressurized containers, electrical and optical cables, especially when such reinforced products are used in deep water environments, where reinforcement is required to support the load of reinforced products when they are lifted. The invention, therefore, also relates to a coating and a reinforced product containing reinforcement elements, or containing said coating, wherein the reinforcement elements or the coating contain the UHMWPE fibers of the invention.
    More preferably, the UHMWPE fibers of the invention are employed in applications where said fibers experience static tension or static loads and in particular long-term and ultra-long static tension or static loads. The term static tension in this document means that the fiber in application is always or most often under tension, regardless of whether the tension is at a constant level (for example, a weight hanging freely on a rope comprising the fiber) or level variable (for example, if exposed to thermal expansion or movement of water waves). Examples of applications where static stresses are found are, for example, many medical applications (for example, cables and sutures), but also mooring cables, and tension reinforcing elements, since the improved deformation duration of the present fibers leads better performance and similar applications.
    A particular application of the UHMWPE fibers of the invention is found in crane pulleys, where the pulley can reach a high temperature, as a result of: (1) ambient temperatures and / or (2) internal heat generation due to friction around of the crane pulleys.
    Therefore, the invention relates to the ropes and, in particular, to the mooring cables, with or without a cover, which contain the UHMWPE fibers of the invention. Preferably, at least 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight of the total weight of the fibers used to manufacture the rope and / or the coating are made up of UHMWPE fibers from invention. More preferably, the weight of the fibers used to make the rope and / or the jacket is made up of UHMWPE fibers of the invention. The remaining weight percentage of the fibers of the cable according to the invention may contain fibers or combinations of fibers made of other materials suitable for the manufacture of fibers, such as, for example, metal, glass, carbon, nylon, polyester, aramid, others types of polyolefins and the like.
    The invention additionally relates to composite articles containing the UHMWPE fibers of the invention.
    In a preferred embodiment, the composite article contains at least one monolayer comprising the UHMWPE fibers of the invention. The term monolayer refers to a layer of fibers, for example, fibers in a plane. In another preferred embodiment, the monolayer is a unidirectional monolayer. The term unidirectional monolayer refers to a layer of unidirectionally oriented fibers, that is, fibers in a plane that are essentially oriented in parallel. In yet another preferred embodiment, the composite product is the multilayer composite article, containing a plurality of unidirectional monolayers, the direction of the fibers in each monolayer being preferably rotated at a certain angle with respect to the direction of the fibers in an adjacent monolayer. Preferably, the angle is at least 30 °, more preferably at least 45 °, even more preferably at least 75 °, most preferably the angle is about 90 °. Multilayer composite articles have proven their good use in ballistics applications, for example, bulletproof vests, helmets, shields, rigid and flexible panels, vehicle armor panels and the like. Therefore, the invention also relates to bulletproof articles such as those enumerated above, containing UHMWPE fibers of the invention.
    The UHMWPE fibers of the invention are also suitable for use in medical devices, for example, sutures, cables used in medicine, medical implants, surgical repair products and the like. The invention, therefore, relates, in addition, to a medical device, in particular to a surgical repair product and more specifically, to a suture and a medical cable comprising the UHMWPE fibers of the invention.
    It was also observed that the UHMWPE fibers of the invention are also suitable for use in other applications, such as, for example, synthetic chains, conveyor belts, tension structures, concrete reinforcements, fishing lines and nets, nets for soil containment, nets for loads, curtains, kite lines, dental floss, tennis racket strings, tarpaulins (for example, tent canvas), non-woven fabrics and other types of fabrics, straps, battery separators, capacitors, pressure vessels (eg example, inflatable pressure cylinders), hoses, mooring cables (offshore), electrical cables, optical fiber and signal cables, automotive equipment, power transmission belts, building materials, knife cut resistant materials and incision-resistant articles, protective gloves, composite sports equipment, such as skis, helmets, kayaks, canoes, bicycles and boat hulls and stringers, speaker cones, is high performance electrical equipment, dome, boat sails, geotextiles, such as carpets, bags, hammocks and the like. Therefore, the invention also relates to the applications listed above, containing the UHMWPE fibers of the invention.
    The invention also relates to an elongated object that comprises a plurality of UHMWPE fibers of the invention, wherein said fibers are at least partially fused together. In one embodiment, said elongated object is a monofilament. In a different embodiment, said elongated object is a ribbon. The phrase at least partially condensed fibers is understood in the present document by individual fibers which are fused in several places along its length and disconnected between said positions. Preferably, said fibers are fully fused together, that is, the individual fibers are fused together essentially along their entire length. Preferably, the melting is carried out, at least, by compressing said plurality of UHMWPE fibers under a temperature below the melting temperature of the fibers. The melting temperature of the fibers can be determined by DSC using a methodology as described on page 13 of WO 2009/056286. The processes for melting UHMWPE fibers into monofilaments and tapes are known in the art and disclosed, for example, in WO 2004/033774, WO 2006/040190 and WO 2009/056286. It was observed that, using the fibers of the invention, monofilaments and tapes with improved deformation properties are obtained. Such products are suitable for use in applications such as fishing lines, linings, reinforcement elements; bulletproof items, such as armor, car parts, and architectural applications, such as doors.
    The figures will be explained below:
    Figure 1 shows a configuration used to determine the duration of the deformation of the UHMWPE fibers of the invention.
    Figure 2 shows a graphical representation of the deformation rate [1 / s] on a logarithmic scale, versus the percentage elongation characteristic [%] with respect to an investigated yarn.
    The invention will be further explained by the following examples and comparative experiments, however, firstly, the methods used to determine the various parameters employed above will be presented. MEASUREMENT METHODS: - IV: The intrinsic viscosity for UHMWPE is determined according to ASTM D1601-99 (2004) at 135 ° C in decalin, with a dissolution time of 16 hours, with BHT (butylated hydroxytoluene) as an antioxidant in an amount of 2 g / L of solution. The IV is obtained by extrapolating the viscosity, measured in different concentrations to zero concentration. - Dtex: fiber title (dtex) was measured by weighing 100 meters of the fiber. The fiber decitex was calculated by dividing the weight in milligrams to 10; - Fiber tensile properties: Tensile strength (or force) and modulus of elasticity (or modulus) and elongation at break are defined and determined in multi-filament yarns, as specified in ASTM D885M, using a nominal gauge length of the 500 mm fiber, a crosshead speed of 50% / min and Instron 2714 clamps, of the type “Fiber Grip D5618C". Based on the measured stress-strain curve, the modulus of elasticity is determined as a gradient between 0.3 and 1% deformation.To calculate the modulus and the force, the measured tensile forces are divided by the title, as determined by weighing 10 meters of fiber; values in GPa are calculated assuming a density of 0.97 g / cm3 - Tensile properties of fibers having a ribbon-like shape: tensile strength, modulus of elasticity and elongation at break are defined and determined at 25 ° C on tapes with a width of 2 mm, as specified in ASTM D882, uses with a nominal tape gauge length of 440 mm, with a crosshead speed of 50 mm / min. - Number of olefinic branches, for example, ethyl or butyl per thousand carbon atoms: was determined by FTIR in a 2 mm thick compression molded film by quantifying the absorption at 1,375 cm-1 using a calibration curve based on in NMR measurements such as EP 0 269 151 (specifically page 4 of the same). - Elongation stress (ES in N / mm2) of a UHMWPE, it is measured according to the ISO 11542-2A standard. - Deformation duration and elongation in deformation duration were determined according to the methodology described in the document "Predicting the Creep Lifetime of HMPE Mooring Rope Applications” by MP Vlasbloom and RLM Bosman - Proceedings of the MTS / IEEE OCEANS 2006 Boston Conference and Exhibition , held in Boston, Massachusetts on September 15-21, 2006, Session Ropes and tension Members (Wed 1:15 PM - 3:00 PM) More specifically, the duration of the deformation can be determined with a device, as depicted schematically in figure 1, in separate yarn samples, that is, yarns with substantially parallel filaments, about 1,500 mm in length, containing a titer of about 504 dtex and consisting of 900 filaments. similar to the tape that needs to be investigated, fibers were used that have a width of about 2 mm.The yarn samples were tightened without sliding between two clips (101) and (102) by winding each end of the wire several times around the axis of the clamps and then tying the free ends of the wire to the wire body. The final length of the wire between the clamps (200) was about 180 mm. The attached wire sample was placed in a temperature-controlled chamber (500) at a temperature of 70 ° C by attaching one of the clamps to the chamber ceiling (501) and the other clamp to a counterweight (300) of 3,187 g resulting in a load of 600 MPa on the wire. The position of the clamp (101) and that of the clamp (102) can be read on the scale (600) marked in centimeters and subdivided in mm, with the help of the indicators (1011) and (1021). Particular attention was paid to placing the wire inside the said chamber, to ensure that the wire segment between the clamps does not touch any of the device's components, so that the experiment can be carried out completely frictionless. An elevator (400) below the counterweight has been employed to raise the counterweight to an initial position, whereby, no yarn loosening occurs and no initial load is applied to the yarn. The starting position of the counterweight is the position where the length of the wire (200) is equal to the distance between (101) and (102) as measured in (600). The wire was subsequently preloaded with a full load of 600 MPa, for 10 seconds by lowering the elevator, after which the load was removed, by lifting the elevator back to its initial position. The yarn was subsequently relaxed for a period of 10 times the preload time, i.e., 100 seconds. After the pre-loading sequence, the full charge was applied again. The elongation of the wire over time was monitored on the scale (600) by reading the position of the indicator (1021). The time required for the indicator ditto to advance 1 mm was recorded for each 1 mm stretch, until the wire broke. The elongation of wire ε, [in mm] at a given time is understood here as the difference between the length of the wire between the clamps at that moment t, that is, L (t) and the initial length (200) of the wire L0 between the staples.
    Yarn elongation (in percent) is:

    The strain rate [in 1 / s] is defined as the change in wire length per time step and was determined according to formula (2), as:
    where εi and εi-1 are the stretches (in%) at the moment ie at the previous moment i-1; etet ii are the time (in seconds) required for the wires to reach the elongations εi and εi-1 respectively. The strain rate [1 / s] was then plotted on a logarithmic scale, against elongation in percentage [%] to obtain a graph (100), as shown in figure 2. The minimum value (1) of the The graph in figure 2 was then determined and the linear portion (2) of it after said minimum (1) received the addition of a straight line (3) that also contained the minimum (1) of the graph. The stretch (4) at which the graph (100) begins to deviate from the straight line was used to determine the time when the stretch occurred. This time was considered as the deformation duration for the wire under investigation. Said elongation (4) was considered to be the elongation for the duration of the deformation. PREPARING THE UHMWPE Classification a)
    A batch polymerization process was carried out in a 55 liter stainless steel reactor equipped with a mechanical stirrer. The reactor was charged with 25 liters of dry heptane and then heated to 60 ° C. The temperature was controlled by a thermostat. Subsequently, the reactor was charged with 96.25 NL of 1-butene, 3.30 mL (0.5 mol / L) TEOS; and 12.65 ml (2 mol / L) of TEA.
    The reactor was subsequently pressurized with ethylene gas to 200 kPa using an ethylene flow of about 1,800 NL / h. Once the 200 kPa pressure was obtained, 10.36 mL (65 mg / mL) of Ziegler-Natta was added to the reactor. The reactor was subsequently pressurized with ethylene to 500 kPa, using a flow of 1,800 NL / h, and maintained at that pressure for 15 minutes. Thereafter, ethylene was added to the reactor with a maximum flow of 1,800 NL / h until the desired total amount of ethylene has been metered (7,700NL).
    After reaching the desired polymerization time (7,700 NL ethylene consumption counts), the polymerization was stopped by cutting off the ethylene supply and the reaction mixture was removed from the reaction vessel and collected in the filter, where the polymer was dried during night by an N2 flow of 100 kPa. The polyethylene produced according to the process described above had an ES of 0.48, 0.69 branches of ethyl per thousand carbon atoms and an IV of about 25 dl / g. Classification b)
    The polymerization process described immediately above, related to classification a), was repeated, however, only 1.65 mL (0.5 mol / L) of TEOS was used. The polyethylene produced according to this process had an ES of 0.39, 1.05 ethyl branches per thousand carbon atoms and an IV of about 19 dl / g. Classification c)
    A batch polymerization process was carried out in a 55 liter stainless steel reactor equipped with a mechanical stirrer. The reactor was charged with 25 liters of dry heptane and 550 ml of dry 1-hexene then heated to 65 ° C. The temperature was controlled by a thermostat. Subsequently, the reactor was charged with 6.0 mL (0.4 mol / L) TEOS; and 12.15 ml (2 mol / L) TEA.
    The reactor was subsequently pressurized with ethylene gas to 200 kPa using an ethylene flow of about 2,300 NL / h. Once the 200 kPa pressure was obtained, 12.4 mL (68.18 mg / mL) of Ziegler-Natta was added to the reactor. The reactor was subsequently pressurized with ethylene to 400 kPa, using a flow of 2,300 NL / h, and maintained at that pressure for 15 minutes. Subsequently, polymerization was carried out under an ethylene flow of approximately 2,300 NL / h.
    After reaching the desired polymerization time (7,700 NL ethylene consumption counts), the polymerization was stopped by cutting off the ethylene supply and the reaction mixture was removed from the reaction vessel and collected in the filter, where the polymer was dried during night by an N2 flow of 100 kPa. The polyethylene produced according to the process described above had an ES of 0.42, 0.31 branches of ethyl per thousand carbon atoms and an IV of about 21 dl / g. Classification d)
    The polymerization process described immediately above and related to classification c) was repeated, however, 1,400 ml of dry 1-hexene was added and 3 ml (0.4 mol / L) of TEOS were added. The polyethylene produced according to this process had an ES of 0.41, 0.53 n-butyl branches per 1,000 carbon atoms and an IV of about 21 dl / g. COMPARATIVE EXPERIMENT
    A 5% solution by weight of a UHMWPE (sold by Ticona as GUR 4170) in decal was obtained, said UHMWPE having an IR of 21 dl / g, as measured in solutions in decal at 135 ° C. Said UHMWPE did not appear to contain any ethyl or butyl branches that could be measurable with the branch measurement method employed in accordance with the invention.
    A process such as that described in WO 2005/066401 was employed to produce UHMWPE fibers. Specifically, the UHMWPE solution was extruded with a 25 mm twin-screw extruder equipped with a gear pump at an adjusted temperature of 180 ° C through a spinner with a number n of 390 rotation holes in an air atmosphere containing also decalin and water vapors at a rate of about 1.5 g / min per hole.
    The rotation holes had a circular cross section and consisted of a gradual decrease in the initial diameter from 3.5 mm to 1 mm, with a cone angle of 60 ° C followed by a section of constant diameter with L / D of 10, this specific geometry of the rotation holes introducing a drag rate in the DRsp spinner of 12.25.
    From the spinneret, the fluid fibers entered a 25 mm air gap, and into a water bath, where the fluid fibers were removed at such a rate that the rate of entrainment of the UHMWPE fluid filaments, Fluid of 277 was obtained.
    The fluid fibers were cooled in a water bath to form gel fibers, the water bath being maintained at about 40 ° C and where a flow of water was being provided with a flow rate of around 50 liters / hour perpendicular to the fibers entering the bath. From the water bath, the gel fibers were taken to an oven at a temperature of 90 ° C, where the evaporation of the solvent occurred to form solid fibers.
    The solid fibers were dragged in a first stage at around 130 ° C and in a second stage at around 145 ° C by applying a total solid drag rate (solid DR) of about 26.8, during which process the most of the decalin has been evaporated. The total solid drag rate is the product of the solid drag rates used in the first stage and in the second stage of the drag.
    The total DRtotal stretch ratio (= fluid flu x DR gel) was 277 x 1 x 26.8 = 7,424. EXAMPLE 1
    The Comparative Experiment was repeated with the UHMWPE prepared as exemplified above in Classification a). A solution of 7.74% by weight was employed and spun through a spinner having 64 holes with a rate of 1.43 g / min / hole. The rotation holes had a gradual decrease in the initial diameter from 3.0 mm to 1.0 mm, introducing DRsp of 9. The air gap was 15 mm and the fluid was 141. The water bath was maintained at about 30 ° C and the water flow was about 50 liters / hour. The gel fibers were dried at about 95 ° C and the solid fibers were stretched in a four step process to reach a solid DR of around 18. Total DR was 2,468. EXAMPLE 2
    Example 1 was repeated with the UHMWPE prepared as exemplified above in classification b) however, solid DR was about 17 and total DR was 2,397. EXAMPLE 3
    Example 1 was repeated with the UHMWPE prepared according to the example exemplified above in classification c) and using a solution of 6.73% by weight. Solid DR was around 15 and total DR was 2,115. EXAMPLE 4
    Example 3 was repeated with the UHMWPE prepared as exemplified above in classification d) however, solid DR was about 10 and total DR was 1,410.
    The properties of the fibers of the Comparative Example and the Examples, that is, the duration of deformation, tensile strength and modulus together with the properties of some commercially available fibers, ie SK75 and SK78 from DSM Dyneema and Spectra 1000 and 2000 from Honeywell US are summarized in Table 1. In the table it can be seen that the fibers of the invention have an incomparable deformation duration. In addition, the elongation at break (in%) of the fibers of Examples 1-4 was 3.7; 3.3; 3.5 and 3.8, respectively, and thus lower than the samples used for comparison, which were greater than about 5%. Table 1

    权利要求:
    Claims (12)
    [0001]
    1. Ultra-high molecular weight polyethylene fiber (UHMWPE) with improved deformation obtained by spinning a UHMWPE having an intrinsic (IV) viscosity of at least 19 dl / g, characterized by comprising ethyl branches or butyl branches and presenting an elongation stress (ES) measured according to ISO 11542-2A, where if fiber is obtained by spinning a UHMWPE comprising ethyl branches, the ratio (C2H5 / 1,000C) / (ES) between the number of branches of ethyl per thousand carbon atoms (C2H5 / 1,000C) and the elongation stress (ES) is between 1.00 and 3.00, in which the said UHMWPE fiber when subjected to a load of 600 MPa at a temperature of 70 ° C, has a deformation duration of at least 125 hours, or where if the fiber is obtained by spinning a UHMWPE comprising butyl branches, the ratio (C4H9 / 1,000C) / (ES) between the number of branches butyl per thousand carbon atoms (C4H9 / 1,000C) and the stretching stress (ES) is between 0.2 and 3.0, wherein said UHMWPE fiber when subjected to a load of 600 MPa, at a temperature of 70 ° C, has a deformation duration of at least 90 hours.
    [0002]
    2. Fiber, according to claim 1, characterized by the fact that the deformation duration is at least 290 hours.
    [0003]
    3. Fiber according to claim 1 or 2, characterized by the fact that the deformation duration is at least 350 hours.
    [0004]
    Fiber according to any one of claims 1 to 3, characterized in that it is obtained by a gel spinning process.
    [0005]
    5. Fiber according to any one of claims 1 to 4, characterized by the fact that the UHMWPE has an ES of at most 0.50.
    [0006]
    6. Fiber, according to claim 1, characterized by the fact that the UHMWPE has an amount of ethyl branches per thousand carbon atoms (C2H5 / 1,000C) between 1.20 and 2.80.
    [0007]
    Fiber according to any one of claims 1 to 6, characterized by the fact that UHMWPE is obtained by a suspension polymerization process in the presence of an olefin polymerization catalyst.
    [0008]
    8. Fiber, according to claim 7, characterized by the fact that the polymerization process comprises the following sequence of steps: a) loading a stainless steel reactor with: i. a non-polar aliphatic solvent having a boiling point under standard conditions, above that of the polymerization temperature, wherein said polymerization temperature is preferably between 50 ° C and 90 ° C; wherein said boiling point of said solvent is between 60 ° C and 100 ° C; ii. an alkyl aluminum, as a cocatalyst; iii. ethylene gas at a pressure between 10 and 500 kPa.g; iv. 1-butene, in a gas: total ethylene ratio (NL: NL) of at most 325: 1, preferably at most 150: 1, even more preferably at most 80: 1, where Total ethylene means ethylene added in steps a) -iii) and b) or 1-hexene; v. a Ziegler-Natta catalyst suitable for producing UHMWPE under conditions a) -i) to a) -iv); b) gradually increase the pressure of the ethylene gas inside the reactor to achieve a maximum ethylene gas pressure of 1,000 kPa.g, during the course of the polymerization process; and c) polymerization of UHMWPE molecules so that they produce UHMWPE particles having an average particle size (D50) as measured by ISO 13320-1 of between 80 μm and 300 μm.
    [0009]
    9. Rope, crane pulley, mooring rope or ropes, characterized by comprising the fiber, as defined in any one of claims 1 to 8.
    [0010]
    10. Reinforced product containing reinforcement elements, characterized by the fact that the reinforcement elements contain the fiber, as defined in any one of claims 1 to 8.
    [0011]
    11. Multilayer composite articles for applications in bulletproof articles, for example, vests, helmets, rigid and flexible armor panels and vehicle armor panels, characterized by the fact that said articles contain fiber, as defined in any one of claims 1 to 8.
    [0012]
    12. Product containing the fiber, as defined in any one of claims 1 to 8, characterized by the fact that said product is selected from the group consisting of fishing lines and fishing nets, nets for soil containment, nets for loads and curtains, kite lines, dental floss, tennis racket strings, tarpaulins, non-woven and woven fabrics, belts, battery separators, capacitors, pressure vessels, hoses, mooring cables, automotive equipment, power transmission belts , materials for construction of 5 buildings, articles resistant to knife cuts and articles resistant to incision, protective gloves, composite sports equipment, skis, helmets, kayaks, canoes, bicycles and hulls of boats and stringers, speaker cones, electrical insulation high performance, 10 bellows, boat sails and geotextiles.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112013026052B1|2020-12-29|ultra-high molecular weight polyethylene fiber, rope, crane pulley, mooring rope or twine, reinforced product containing reinforcement elements, multilayer composite articles and product containing the fiber
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    JP2021177025A|2021-11-11|Low creep fiber
    同族专利:
    公开号 | 公开日
    US20140106104A1|2014-04-17|
    EA028681B1|2017-12-29|
    CA2832934A1|2012-10-18|
    CN103608501B|2016-08-31|
    WO2012139934A1|2012-10-18|
    BR112013026052A2|2020-07-07|
    NO2697414T3|2018-02-03|
    LT2697414T|2017-12-27|
    CN106245135B|2018-10-16|
    EA028681B8|2018-02-28|
    MX349304B|2017-07-20|
    EA201301155A1|2014-03-31|
    JP6069676B2|2017-02-01|
    KR20140022067A|2014-02-21|
    KR101927561B1|2018-12-10|
    EP2697414B1|2017-09-06|
    EP2697414A1|2014-02-19|
    US9534066B2|2017-01-03|
    ES2644121T3|2017-11-27|
    MX2013011877A|2013-11-01|
    CN103608501A|2014-02-26|
    JP2014510851A|2014-05-01|
    CN106245135A|2016-12-21|
    CA2832934C|2019-08-20|
    PT2697414T|2017-10-24|
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    法律状态:
    2020-07-14| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/04/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11162246|2011-04-13|
    EP11162246.0|2011-04-13|
    PCT/EP2012/056079|WO2012139934A1|2011-04-13|2012-04-03|Creep-optimized uhmwpe fiber|
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