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    • 专利摘要:
    High Strength Coated Fibers The invention relates to high strength fibers comprising a crosslinked silicone polymer coating and fabricated cables thereof. the fibers are preferably high performance polyethylene (hppe) fibers. The coating comprising a crosslinked silicone polymer is manufactured from a crosslinkable coating composition. comprising a silicone polymer the cable shows markedly improved service life in bending applications such as cyclic bending specimen applications. The invention also relates to the use of a crosslinked silicone polymer in a cable for improved flexural fatigue strength.
    公开号:BR112012002556B1
    申请号:R112012002556-2
    申请日:2010-07-26
    公开日:2019-11-05
    发明作者:Aben Gerardus；Schneiders Hans；Bosman Rigobert
    申请人:Dsm Ip Assets Bv；
    IPC主号:
    专利说明:

    HIGH-RESISTANCE COATED FIBERS
    The invention relates to coated high strength fibers and the use of such fibers to make a cable. Such a cable is specifically suitable for applications involving repeated flexing of the cable. The invention also relates to the method of manufacturing the coated fibers and cable.
    Applications that involve repeated flexing of a cable, hereinafter also referred to as bending applications, include applications in specimens subjected to bending. A cable for applications in test pieces subjected to bending is within the context of this application considered to be a cable carrying a load typically used in lifting or installation applications, such as marine, oceanographic, oil and offshore gas, seismic, commercial fishing and other industrial markets. During these uses, referred to together as applications in specimens subjected to bending, the cable is often pulled over ^ ___ posts, __ pulleys ^, --- pulleys -, - etc - ^, --- a. O. resulting in friction and flexing of the cable. When exposed to such frequent bending or flexing, a cable may fail due to damage to the cable and fiber resulting from external and internal abrasion, frictional heating, etc .; such fatigue failure is referred to as curvature fatigue or flexion fatigue.
    A disadvantage of known cables remains a limited service life when exposed to frequent bending or flexing. Consequently, there is a need in the cable industry to show improved performance in bending applications over extended periods.
    In order to reduce, among others, the loss of strength resulting from the internal friction between the fibers in the cable, the application of a specific mixture of polymer fibers in the cable wires is proposed in US 6,945,153 B2. US
    6,945,153 B2 describes a braided construction cable, where the strands contain a mixture of high-performance polyethylene fibers and lyotropic or thermotropic polymer fibers, in a ratio of 40:60 to 60:40. Lyotropic or thermotropic liquid crystalline fibers, such as aromatic polyamides (aramides) or polyisoxazoles (PBO) are indicated to provide good resistance to rupture deformation, but also because they are very susceptible to self-abrasion, considering that the fibers of HPPE are mentioned to exhibit the least amount of fiber-to-fiber abrasion, but also because they are prone to slip failure.
    The cables to be used in flexural test specimen rupture applications that comprise high tenacity polyolefin fibers are known from -2-0 --- WQ-2O £ 7 - / - l-01032 —e — WQ2- ÚÚ7 / 062803. — Νθ — ΝΘ2ΌΌ 2 7 / 1ΌΐΟ3-2— © cable is constructed from fibers coated with a (liquid) composition comprising an amino functional silicone resin and a low molecular weight neutral polyethylene wax. WQ2007 / 062803 describes a cable constructed from 25 high-performance polyethylene fibers and polytetrafluoroethylene fibers. The cable can contain 3-18% by weight of silicone compounds that are fluid polyorganosiloxanes.
    Thus, according to the prior art, it has been suggested the use of liquid silicone compositions, also known as silicone oils, to the high resistance coating fibers to be used in cables for applications in test pieces subjected to bending. A disadvantage of such an oil is that, when the cable is placed under tension and with increasing temperature, the silicone oil tends to be pushed out of the cable, and thus loses its beneficial effect on the performance of the cable.
    The aim of the invention is, therefore, to provide a high strength fiber and a cable made of such high strength fiber 10 that has improved properties for bending applications. Another objective is to provide a cable that has improved properties for bending applications.
    This object is achieved according to the invention with a high-strength fiber coated with a cross-linked silicone polymer. The coating is preferably made of a coating composition comprising a crosslinkable silicone polymer.
    The advantages of large coated fibers
    2 - resistance - of - the invention - are - an improved - protection - to the - abrasion of the fibers, when a cable is made of such fibers. In addition, the use of a cross-linked or cured silicone coating results in a coating that is not removed and can be flexible and heat resistant.
    Specifically, the coating has excellent compatibility with high strength fibers, in particular with HPPE fibers.
    It has been found that when the high strength fibers are provided with a coating comprising a crosslinked silicone polymer, a cable made of fibers has surprisingly improved flexural fatigue resistance. The invention thus also provides a cable containing high strength fibers, in which the high strength fibers are coated with a crosslinked silicone polymer.
    According to a second aspect, the invention provides a cable comprising high strength fibers, where the cable is provided with a coating comprising a crosslinked silicone polymer.
    Other advantages of the cable according to the invention include the fact that the cable has a high strength efficiency, which means that the strength of the cable is a relatively high percentage of the strength of its constituent fibers. The cable also shows good traction (storage) and drum type winches, and can be easily inspected for possible damage.
    The present invention, therefore, also relates to the use of a construction and composition cable as detailed — in this —order — as a load-bearing element in bending applications, for example, bending test specimens, such as lifting applications. The cable is best suited for use in applications where a fixed part or parts of the cable are repeatedly bent over an extended period of time. Examples include applications for subsea installations, mining, renewable energy and so on.
    The present invention also relates to the use of a crosslinked silicone polymer in a cable for improving flexural fatigue strength.
    In the present invention, the coating of the high strength fibers or cable is obtained by applying a coating composition comprising a crosslinkable silicone polymer. After applying the coating composition to the fiber or fibers, the coating composition can be cured, for example, by heating to cause crosslinking of the crosslinkable silicone polymer. Crosslinking can also be induced by any other methods suitable for one skilled in the art.
    The temperature for curing the coating composition is 20 to 200 ° C, preferably 50-170 ° C, more preferably 120-150 ° C. The curing temperature should not be too low, so that the curing is effective. If the curing temperature becomes too high, there is a risk that the high strength fiber will deteriorate and lose its strength.
    The weight of the cable or fibers before and after coating followed by curing is measured to calculate the weight of the crosslinked coating. For a fiber, the weight of the crosslinked coating is 1-20% by weight based on the weight 20 --- feeéal of the fiber ^ — preferably ATALO ^ -in-weight Para; As a preference, the weight of the crosslinked jacket is 130% by weight, based on the total weight of the cable and the jacket, preferably 2-15% by weight.
    degree of cross-linking can be controlled. The degree of crosslinking can be controlled, for example, by the temperature of the heating time period. The degree of crosslinking, if carried out in other ways, can be controlled in the methods known to one skilled in the art. The measurement of the degree of cross-linking can be performed as follows:
    cable or fibers provided with the reticulated coating (at least partially) are immersed in a solvent. A solvent is chosen in which the extractable groups (mainly monomers) in the polymer dissolve without being cross-linked and the cross-linked network does not dissolve. A preferred solvent is hexane. When weighing the cable or fibers after immersion in a solvent, the weight of the non-crosslinked portion can be determined and the ratio of the crosslinked silicone 10 to the extractables can be calculated.
    The preferred degree of crosslinking is at least 20%, that is, at least 20% by weight, based on the total weight of the coating that remains on the fibers or cables after extraction with the solvent. More preferably the degree of crosslinking is 30%, more preferably at least 50%. The maximum degree of crosslinking is about 100%.
    Preferably, the crosslinkable silicone polymer comprises a silicone polymer having a reactive end group. It was found that a crosslinking in the 2Ό - terminal-i-s- groups of po-limero-of ~ siltcone-results in a good resistance to flexion. A silicone polymer that is cross-linked in the end groups instead of the branches in the repeating unit results in a less rigid coating. Without being limited to this, the inventors attribute 25 improved cable properties to the less rigid structure of the sheath.
    Preferably, the crosslinkable end group is an alkylene end group, more preferably a C 2 -C 6 alkylene end group. Specifically, the end group is a vinyl group or a hexenyl group. In general, a vinyl group is preferred.
    Preferably, the crosslinkable silicone polymer has the formula:
    CH 2 = CH- (Si (CH 3 ) 2 -O) n -CH = CH 2 (1) where ή is a number of 2-20Õ, preferably del-10, more preferably 20-50.
    Preferably, the coating composition also contains a crosslinker. The crosslinker preferably has the following formula:
    Si (CH 3 ) 3 -O- (SíCH 3 HO) m -Si (CH 3 ) 3 (2) where m is a number n is a number from 2-200, preferably from 1-10, more preferably from 20-50.
    Preferably, the coating composition further comprises a metal catalyst for crosslinking of crosslinkable silicone polymer, the metal catalyst preferably being a platinum, palladium or rhodium, more preferably complex platinum metal catalyst. Such catalysts are known to the person skilled in the art.
    Preferably, the -si-lieone coating composition is a multi-component silicone-s-rs-theme consisting of a first emulsion comprising the crosslinkable silicone polymer and the crosslinker and a second emulsion including the polymer of crosslinkable silicone and metal catalyst.
    Preferably, the weight ratio between the first emulsion and the second emulsion is about 100: 1 to about 100: 30, preferably 100: 5 to 100: 20, preferably more than 100: 7 100: 15.
    Coating compositions as described above are known in the art. They are often referred to as additional curing silicone coatings or coating emulsions. Crosslinking or curing occurs when the vinyl end groups react with the SiH group on the crosslinker. ___ ____________
    Examples of such coatings are Dehesive® 430 (crosslinker) and Dehesive® 440 (catalyst) from Wacker Silicones; Emulsion 912 from Silcolease® and Catalyst 913 Silcolease® from Bluestar Silicones, and Emulsion Coating Syl-off® 7950 and Catalyst Emulsion Syl-off® 7922 10 from Dow Corning.
    An additional advantage of the invention is that the crosslinked silicone can be used as a vehicle for other functional additives. Thus, the invention also relates to a fiber coated with a crosslinked silicone polymer coating, where the coating also contains an additive, selected from dyes, antioxidants and antifouling agents.
    Such additives are known in the art. Examples of antifouling agents are, for example, copper and -2G - copper complexes, metal pyrithione and carbamate compounds.
    In the context of the present invention, fibers are understood as elongated bodies of indefinite duration and with a dimension of length much greater than width and thickness. The term fiber, thus includes a monofilament, a multiple filament yarn, a strip, a strip or ribbon and the like, and can have a regular or irregular cross section. The term fibers also includes a plurality of either or a combination of the above options.
    Thus, according to the invention, the coating of a crosslinked silicone polymer can be applied to the filaments, but also to the multiple filament yarns. In addition, it is also an embodiment of the invention to provide a yarn, including ____ high strength ----- 5 fibers, wherein the yarn is coated with a crosslinked silicone polymer.
    Fibers in the form of monofilaments or ribbon-like fibers can be of various titles, but usually have a title in the range of 10 to several thousand dtex, preferably in the range of 100 to 2,500 dtex, more preferably 200 to 2,000 dtex. The multi-strand filament contains a plurality of filaments typically having a titer in the range of 0.2 to 25 dtex, preferably about 0.5 to 20 dtex. The title of a multi-filament yarn can also vary widely, for example, from 50 dtex to several thousand dtex, but is preferably in the range of about 2004,000 dtex, more preferably 300 to 3,000 dtex.
    High strength fibers for use in the invention are 2-0 - the fibers present a tenacity of at least 1.5
    N / tex, more preferably, at least 2.0, 2.5 or even at least 3.0 N / tex. The tensile strength, also simply resistance or toughness of the filaments, is determined by known methods, based on ASTM D2256-97. Generally, such high-strength polymeric filaments also have a modulus of high elasticity, for example, at least 50 N / tex, preferably at least 75, 10 0 or even at least 125 N / tex.
    Examples of these fibers are high-performance polyethylene fibers (HPPE), fibers made from polyamides, for example, poly (p-phenylene terephthalamide) (known as Kevlar®); poly (tetrafluoroethylene) (PTFE); aromatic copolyamide (co-poly- (paraphenylene / 3,4'— oxyphenylene terephthalamide)) (known as Technora®); poly {2,6-diimidazo- [4,5b-4 ', 5'e] pyridinylene-1,4 (2,5dihydroxy) phenylene} (known as M5); poly (p-phenylene2,6-benzobisoxazole) (PBO) (known as Zylon®); liquid crystal thermotropic polymers (LCP), as known for example from US 4,384,016; but also polyolefins other than polyethylene, for example polypropylene homopolymers and copolymers. Also combinations of fibers made from the above-mentioned polymers can be used in the rope of the invention.
    Preferred high strength fibers, however, are HPPE, polyamide or LCP fibers.
    Most preferred fibers are high performance polyethylene (HPPE) fibers. The fibers of HPPE are understood in the present document as fibers made of polyethylene of -28 - weight - uItraTalto (also called ultrahigh molecular weight polyethylene; UHMWPE), and having a toughness of at least 1.5, preferably at least 2.0, more preferably at least 2.5 or even at least 3.0 N / tex. There is no reason for a maximum tenacity limit of the HPPE fibers in the cable, but the fibers available are typically tenacious at most about 5 to 6 N / tex. The HPPE fibers also have a high modulus of elasticity, for example, at least 75 N / tex, preferably at least 100 or at least 3 0 125 N / tex. HPPE fibers are also referred to as high modulus polyethylene fibers.
    In a preferred embodiment, the HPPE fibers in the cable according to the invention are one or more multi-strand filaments. _______ ______ ______ ___
    HPPE fibers, filaments and multiple filament yarns can be prepared by spinning a solution of UHMWPE in an appropriate solvent on gel fibers and dragging the fibers before, during and / or after partial or total removal of the solvent, ie through a process called gel spinning. Gel spinning of a solution is well known to one skilled in the art and is described in numerous publications including, EP 0205960 A, EP 0213208 Al, US 4413110, GB 2042414 A, EP 0200547 Bl, EP 0472114 Bl, WO 01/73173 Al, and in Advanced Fiber Spinning 15 Technology, Ed. T. Nakajima, Woodhead Publ. Ltd (1994, ISBN 1-855-73182-7, and references cited therein, all incorporated herein by reference.
    HPPE fibers, filaments and multiple filament yarns can also be prepared by 2Ό melt-spinning UHMWPE, although the mechanical properties, such as toughness, are more limited compared to HPPE fibers manufactured by the gel spinning process. The upper limit of the molecular weight of the UHMWPE, which can be spun by melting, is lower than the limit with the gel spinning process. The melt spinning process is widely known in the art, and involves heating a PE composition to form a PE melt, extruding the PE melt, cooling the extruded melt to obtain a solidified PE, and entraining the solidified PE by minus 30 once. The process is mentioned, for example, in
    EP1445356A1 and EP1743659A1, which are hereby incorporated by reference.
    UHMWPE is understood to be polyethylene having an intrinsic viscosity (IV, measured in the decalin solution at 135 ° C) of at least 5 dl / g, preferably between about 8 and 40 dl / g. Intrinsic viscosity is a measure for molar mass (also called molecular weight) that can be more easily determined than actual molar weight parameters, such as, M n and M w . There are several empirical relationships between IV and
    M w , however, this relationship depends on the molar weight distribution. Based on the equation M w = 5.37 * ΙΟ 4 [IV] 1.37 (see EP 0504954 Al) an IV of 8 dl / g would be equivalent to the M w of about 930 kg / mol. Preferably, UHMWPE is a linear polyethylene with less than one branch per 100 carbon atoms, and preferably one branch per 300 carbon atoms, a branch chain or side chain or chain branch generally containing at least 10 atoms of carbon. Linear polyethylene can also contain up to 5 mol% of one or more comonomers, such as, alkenes such as propylene, butene, pentene, 4-methylpentene or octene.
    In one embodiment, the UHMWPE contains a small amount, preferably at least 0.2 or at least 25 0.3 per 1,000 carbon atoms, from relatively small groups, such as pendant side groups, preferably an alkyl group Ci-C 4 . Such fiber shows an advantageous combination of high strength and slip resistance. A very large side group or a very high number of side groups, however, negatively affects the fiber manufacturing process. For this reason, the UHMWPE preferably contains methyl or ethyl side groups, more preferably methyl side groups. The number of side groups is preferably at most 5 maximum 20, more preferably at most 10, 5 or at most 3 per 1,000 carbon atoms.
    The HPPE fibers in the cable according to the invention may also contain small amounts, generally less than 5% by weight, preferably less than 3% by mass of usual additives, such as antioxidants, thermal stabilizers, dyes, promoters of flow, etc. The UHMWPE can be a simple classification polymer, but also a mixture of two or more different polyethylene classifications, for example, differing in IV or molar weight distribution, and / or type and number of comonomers or secondary groups.
    The cable according to the invention is a cable especially suitable for bending applications, such as applications in specimens subjected to bending. A 2nd head with a large diameter, for example, of at least 16 mm is suitable for certain bending applications. The cable diameter is measured at the outermost circumference of the cable. This is due to the irregular limits of the cables defined by the wires. Preferably, the cable according to the invention is a resistant cable with a diameter of at least 30 mm, more preferably at least 40 mm, at least 50 mm, at least 60 mm, or even at least 70 mm. Larger known cables have diameters up to about 300 mm, the cables used in installations in deep waters typically have a diameter of up to about 130 mm.
    The cable according to the invention can have a cross section that is circular or round, but also an oblong cross section, which means that the cross section 5 of a tensioned cable shows a flattened, oval shape, or even (depending on the number primary yarns) an almost oblong shape. Such an oblong cross section preferably has an aspect ratio, that is, the ratio of the largest diameter to the smallest (or ratio of 10 width to height), in the range of 1.2 to 4.0. Methods for determining the aspect ratio are known to those skilled in the art; an example includes measuring the external dimensions of the cable, keeping the cable taut, or after wrapping it tightly with adhesive tape around it. The advantage of a non-circular section with the said aspect ratio is that, during cyclic bending where the direction of the cross section width is parallel to the direction of the pulley width, less tension differences occur between the fibers in the cable and less abrasion and frictional heat 0 occur, resulting in an improved flex fatigue life. The cross section preferably has a ratio of about 1.3 to 3.0, more preferably about 1.4 to 2.0.
    In the case of a cable with an oblong cross section, it is more correct to define the size of a cable loop by the diameter of a cable loop of the same weight by length than in relation to a non-cable loop, sometimes referred to in the industry as the effective diameter. In this document, the term diameter means an effective diameter 30 in the case of a cable with an oblong cross section.
    Preferably, the cable and / or fibers in the cable are further coated with a second layer to further improve flexion fatigue. Such coatings, which can be applied to the fibers prior to construction of the cable, or to the cable after it has been constructed, are known and examples include coatings comprising silicone oil, bitumen and both. The polyurethane-based coating is also known, possibly mixed with silicone oil. The cable preferably contains the second coating of 2.5 to 35% by weight in a dry state. More preferably, the cable contains 10 to 15% by weight of the second coating.
    In one embodiment of the present invention, the cable further includes synthetic fibers made from a polymer other than HPPE. These fibers can be of various polymers suitable for the manufacture of a fiber, including polypropylene, nylon, aramid (for example, those known by the trademark Kevlar®, Technora®, Twaron®), PBO (polyphenylene benzobisoxazole) (for example, known by the trademark Zylon ®), thermotropic polymer (for example, those known by the trademark Vectran ®) and PTFE (polytetrafluoroethylene).
    PTFE fibers are preferred as additional synthetic fibers. The combination of HPPE fibers and PTFE fibers has been shown to improve the performance of service life in applications, such as in specimens subjected to cyclic flexion as described in example W02007 / 062803A1. PTFE fibers have a toughness that is significantly less than HPPE fibers, and have no effective contribution to the static toughness of the cable. However, PTFE fibers preferably have a toughness of at least 0.3, preferably at least 0.4 or at least 0.5 N / tex, in order to prevent breakage of the fibers during handling , mix with other fibers and / or during cable manufacture. There is no reason for an upper limit on the toughness of PTFE fibers, but the fibers available are typically tough at most about 1 N / tex. PTFE fibers typically have an elongation at break, which is greater than that of HPPE fibers.
    PTFE fiber properties and methods of making such fibers have been described in several publications, including EP 0648869 A1, US 3655853, US 3953566, US5061561, US 6117547, US 5686033.
    The PTFE polymer is understood as a polymer made from tetrafluoroethylene as the main monomer. Preferably, the polymer contains less than 4 mol%, more preferably less than 2 or 1 mol% of monomers, such as ethylene, chlorotrifluorethylene, Tie xafluorpropylene] perfluorpropyl ester and the like. PTFE is generally a very high molecular weight polymer, with a high melting point and high crystallinity, which makes the material melting process practically impossible. Also, its solubility in solvents is very limited. PTFE fibers are therefore normally manufactured by extruding PTFE mixtures and optionally other components below the PTFE melting point in a precursor fiber, for example, a monofilament, tape or sheet, followed by processing steps similar to those of sintering and / or post-stretching of products at elevated temperatures. PTFE fibers, therefore, are typically in the form of one or more monofilament or ribbon-like structures, for example, some ribbon-like structures twisted into a yarn-like product. PTFE fibers generally have a certain porosity, depending on the process applied to manufacture a precursor fiber and the applied post-stretching conditions. Apparent densities of PTFE fibers can vary widely, suitable products 10 having densities in the range of about 1.2 to 2.5 g / cm 3 .
    In a further embodiment of the present invention, the cable is composed of a core element around which the fibers are braided. The construction with a 15-core element is useful when it is desired that the braid does not break in an oblong shape and the cable maintains its shape during use.
    The cable may also contain thermally conductive fibers, such as metal fibers, preferably in the 2nd nucleol. This embodiment is advantageous as long as the center of the cable normally has the highest temperature. With this embodiment, the heat generated and otherwise kept in the center of the cable is dissipated especially quickly along the longitudinal direction. For applications 25 where the same part of the cable is repeatedly exposed to bending, this is especially advantageous.
    Preferably, the weight ratio of the HPPE fibers is 98% to the total fibers in the cable. The strength of the cable depends largely on the amount of HPPE 30 fibers in the cable as the HPPE fibers contribute more to the strength.
    In embodiments comprising a blend of HPPE fibers and other fibers, such as additional synthetic fibers, as described above, the blend of fibers 5 can be at all levels. The mixture may be in strands made of fibers, strands made of strands of the cable, and / or the final strand made of strands. Some embodiments are shown below to illustrate the possible constructions of the cable. It is noted that these 10 embodiments are for illustrative purposes only and do not show all possible mixtures within the scope of the present invention.
    In one embodiment, different types of fibers are formed on a cable wire. The cable wires are made from filaments and the filaments are made from the final composite cable.
    In a further embodiment, each cable strand is made from a single type of fiber, that is, a first strand of cable is made from the first fibers and a second
    --eabcr-é- fabrroadõ - of the second fibers and so on. The first, second strands and optional and additional cable strands are made from filaments and the filaments are made from the final composite cable.
    In a further embodiment, each strand of cable is manufactured from a single type of fibers. Each wire is manufactured from a single type of cable wire. The filaments manufactured from each different type of fibers are manufactured in the final composite cable.
    In a further embodiment, some strands of cable or filaments are made from one type of fibers and some strands of cable or filaments are made from two or more types of fibers.
    The cable according to the invention can be of various constructions, including deposition, braided, parallel (with sheath), and cables constructed as steel cables. The number of filaments in the cable can also vary widely, however, in general, it is at least 3 and preferably at most 16 to arrive at a combination of good performance and ease of manufacture.
    Preferably, the cable according to the invention is of a braided construction, to provide a robust and torque-balanced cable that maintains its coherence during use. There are a variety of known braid types, each generally distinguished by the method that forms the cable. Suitable constructions include sutache braids, tubular braids, flat braids. Tubular or circular braids are the most common braids for cable applications and generally consist of two sets of filaments that intertwine, with different patterns “TpoHSiveisí The number of filaments in a tubular braid can vary widely. Especially if the number of lines is high and / or if the filaments are relatively thin, the tubular braid can have a hollow core, and the braid can break into an oblong shape.
    The number of filaments in a stranded cable according to the invention is preferably at least 3. There is no limit to the number of filaments, although in practice, the cables generally have no more than 32 filaments. Specifically suitable are cables of a braided construction of 8 or 12 filaments. Such cables provide a favorable combination of toughness and flex fatigue strength, and can be manufactured economically on relatively simple machines.
    The cable according to the invention can be of a _________ construction in which the deposition length (the length of one turn of a filament in a deposition construction) or the interlacing period (which is the step length) related to the width braided cable) is not specifically important. Appropriate deposition lengths and entanglement periods are in the range of 4 to 20 times the diameter of the cable. A longer deposition length or interlacing period can result in a looser cable with greater resistance, but being less robust and more difficult to join. A very short deposition length or entanglement period can greatly reduce toughness. Preferably, therefore, the deposition length or entanglement period is about 5 to 15 times the cable diameter, more preferably 6 to 10 times the cable diameter. ___
    -20 ------- No — Cãbõ de ãcõrdõ with the invention the construction of the filaments, also referred to as primary filaments is not specifically important. The person skilled in the art can select suitable constructions such as deposed or stranded filaments and the twisting factor or interlacing period respectively, such that it results in a torque-free and balanced cable.
    In a special embodiment of the invention, each primary filament is properly a braided cable. Preferably, the filaments are circular filaments made of an even number of secondary filaments, also called cable threads, which comprise polymeric fibers. The number of secondary filaments is not limited and can vary, for example, from 6 to 32; with 8, 12 or 16 being preferred in view of the available machinery ---------- for making such braids. One skilled in the art can choose the type of construction and title of the filaments in relation to the desired final construction and cable size, based on their knowledge or with the help of some calculations or experimentation.
    The secondary filaments or strands of the cable containing polymeric fibers can be of various constructions, again depending on the desired cable. Appropriate constructions include twisted fibers; however, braided cables or cables such as a circular braid can also be used. Suitable constructions are mentioned, for example, in US 5901632.
    The cable according to the invention can be manufactured with known techniques for assembling a cable from polymeric fibers. The coating composition — comprising crosslinkable silicone polymers can be applied to the fibers and cured to form a coating comprising a crosslinked silicone polymer, and then the fibers can be formed into a cable. The coating composition comprising crosslinkable silicone polymers can also be applied after the cable has been manufactured. Of course, it is also possible to apply the coating composition to the cable strands assembled from fibers or over the filaments assembled from the strands of the cable. It is preferable that the coating composition is applied to the fibers before the cable is constructed. The advantage of this is that homogeneous impregnation with the coating composition is obtained on the cable, regardless of the cable diameter.
    A preferred method of making a cable comprising high strength fibers consists of the steps of applying a coating composition comprising a crosslinkable silicone polymer to the high strength fibers and / or the cable and subjecting the high strength fibers and / or the cable at a temperature of 120-150 ° C 10 to form a coating comprising a crosslinked silicone polymer on the cable and / or the HPPE fibers.
    Although the applicability of the fibers of the invention is described primarily for cables, other uses that are known for high strength fibers are also within the scope of the invention. Specifically, fibers can be used to make a net, such as a fishing net. It has been shown that the fibers of the invention have better knot strength compared to uncoated fibers.
    -2 0 -------- The “fibers” can also be woven or otherwise assembled to create fabrics for various applications, such as in the textile industry.
    In addition, the fibers of the invention show improved processability when making cables 25 or other articles except yarns. Better processability means that the yarn containing the fibers of the invention moves smoothly through the machines used to manufacture the cables and little damage occurs to the wires when they come into contact with the different elements of the machine, such as rollers, eyelets etc. . Thus, the threads can be more easily braided or woven.
    Preferably, the coating composition is applied in two stages. In this preferred method, a first emulsion comprising the crosslinkable silicone polymer 5 and a crosslinker is mixed with a second emulsion comprising the crosslinkable silicone polymer and a metal catalyst. The cable and / or fibers are immersed in this mixture. The coating composition is then cured.
    Immersion of the fibers in the coating composition can be carried out during the fiber production process. The fiber production process involves at least one drag stage. The drag stage can take place after the immersion stage.
    The method according to the invention can also comprise, in addition, a post-elongation step of the primary wires before the interlacing step, or, alternatively, a post-elongation step of the cable. Such an elongation step is preferably performed at an elevated temperature, but below the melting point of the
    20 - runners t lower melting) in the filaments (= elongation with heating), preferably at temperatures in the range of 100-120 ° C. Such a post-stretching step is described in a.o. EP 398843 Bl or USA 5,901,632.
    The present invention is described in more detail with reference to the examples.
    Comparative Example A
    A cable with a diameter of 16 mm and made up of HPPE fibers was produced. Dyneema ™ SK75, 1,760 dtex obtained from DSM, Netherlands was used as fiber
    HPPE. The construction of the cable wires was 8 x 1,760 dtex, turns per meter S / Z. Filaments were produced from the threads. The filament construction featured 1 + 6 wire strands, 20 turns per meter Z / S. A cable was produced from the filaments. The construction of the cable had 12 braided filaments with an interlacing period of 109 mm, that is, about 7 times the diameter of the cable. The average cable breaking strength was 22.5 kN.
    The test of rupture of specimens submitted to flexion of the cable was carried out. In this test, the cable was flexed on a free-running pulley having a diameter of 400 mm. The cable was placed under load and cycled back and forth over the pulley until it broke. Each machine cycle produced two linear flexion-linear flexion cycles of the cable section, the double flexion zone. The double flexion stroke was 30 times the cable diameter. The cycling period was 12 seconds per machine cycle. The force applied to the cable was 30% of the average cable breaking strength tested.
    ----- The - cable ~ broke after 1,888 machine cycles.
    Example 1
    The coating composition was prepared from a first emulsion comprising a reactive silicone polymer preformed with a crosslinker and a second emulsion comprising a silicone polymer and a metal catalyst. The first emulsion was an emulsion available from Dow Corning containing 30.0 to 60.0% by weight of dimethyl siloxane terminated with dimethyl vinyl and 1.0 to 5.0% by weight of dimethyl, methylhydrogen siloxane (Syl-off® 7950 Coating Emulsion). The second emulsion was an emulsion available from Dow Corning containing 30.0 to 60.0% by weight of dimethyl siloxane terminated with dimethylvinyl and a platinum catalyst (Syl-off® 7922 Emulsion Coating). The first emulsion and the second emulsion were mixed in an 8.3: 1 weight ratio and diluted with water to a concentration of 4% by weight.
    HPPE fibers, obtained from DSM Holland, such as Dyneema® SK 75, 1,760 dtex, were dipped in the coating composition at room temperature. The fibers were heated in an oven to a temperature of 120 ° C, so that the crosslinking occurred. A cable with the same construction, as described for comparative experiment A, was produced from the coated HPPE fibers.
    The test of rupture of specimens submitted to cable flexion was tested according to the same test method as comparative experiment A. The cable broke after 9,439 cycles of the machine.
    It can be seen, by comparing the results -2-0 - of the —example — compares L i vo ~ A ~ and ~ exemplõ 1 ~ that the test until rupture of specimens subjected to cable flexion was significantly improved through of the cross-linked silicone coating.
    Comparative Example B
    HPPE fibers, obtained from the Netherlands DSM, as
    Dyneema® SK 75, 1,760 dtex, were dipped in a coating composition containing silicone oil (Wacker C800 from Wacker Coating) at room temperature and then dried. A cable with a diameter of 5 mm was produced from the coated HPPE fibers. The construction of the wires was 4 x 1,760 dtex, 20 turns per meter S / Z. A cable was produced from the wires. The construction of the cable consisted of a 12 x 1 filament braided cable and a 27 mm pitch. The cable's average tensile strength was 18,248 N.
    rupture test of specimens submitted to cable flexion was performed. In this test, the cable was flexed on three free-running pulleys with a diameter of 50 mm. The cable was placed under load and cycled back and forth over the pulleys until the cable broke. In a machine cycle, the pulleys were rotated in one direction and then in the opposite direction, thus passing the cable six times over the pulley in a machine cycle. The course of this flexion was 45 cm. The cycling period was 5 seconds per machine cycle.
    The force applied to the cable was 30% of the average cable breaking strength.
    The cable broke after 1313 machine cycles.
    Example 2
    -20 -------- Fibers give ΗΡΤΈ not obtained from the Netherlands DSM, as
    Dyneema® SK 75, 1,760 dtex were coated with the coating composition, as described in Example 1.
    A cable with the same construction, as described for Comparative Experiment B, was built. Its flexion fatigue was tested in the same way as in Comparative Example B. The cable broke after 2,384 machine cycles.
    It can be seen from the results of Comparative Example B and Example 2 that the flexural fatigue strength of the cable has been significantly improved through the crosslinked silicone coating compared to a non-crosslinkable silicone coating.
    Comparative Example C
    A cable with a diameter of 5 mm was produced from HPPE fibers obtained from DSM, Netherlands, such as Dyneema ™ 5 SK75, 1.76Õ dtex. The construction of the cable wires was 4 x
    1,760 dtex, 20 laps per meter S / Z. A cable was produced from the filaments. The constructed cable consisted of a 12 x 1 wire braided cable with a 27 mm pitch. The average cable breaking strength was
    18,750 N. The construction of the filament was 4 x 1,760 dtex.
    test of rupture of specimens submitted to flexion of the cable was carried out in the same way as in Comparative Example B. The cable broke after 347 machine cycles.
    Example 3
    The cable of Comparative Example C was coated with the coating of Example 1 with the proviso that the concentration of the mixed emulsion was 40% solid base. The cable was immersed in the coating composition at room temperature. The cable was heated in an oven to a -20 ° C temperature of Τ20 ° Ό ~, allowing the raw connections to occur.
    In the test of rupture of specimens submitted to the flexing of Comparative Example B the cable broke after 3,807 machine cycles.
    Example 4
    The cable from Comparative Experiment C was coated with a first emulsion: Silcolease® Emulsion 912 and a second catalyst emulsion: Silcolease® Catalyst Emulsion 913 (available from Bluestar Silicones). The first and second emulsions were mixed in a 100: 10 weight ratio and diluted with water to a concentration of 4% by weight. The procedure for applying the coating was the same as in Example 3.
    In the test of rupture of specimens submitted to the flexion of Example B, the cable broke after 1,616 machine cycles.
    Experiments 3 and 4 also show that, when applied to a cable, the cross-linked silicone coating of the invention results in improved bending performance 10 over an uncoated cable (Comparative Example C).
    权利要求:
    Claims (11)
    [1]
    1. High strength fiber coated with a crosslinked silicone polymer, characterized by the fact that the crosslinked silicone polymer is a high performance polyethylene fiber (HPPE), in which the crosslinked degree of the crosslinked silicone polymer is at least minus 20% and in which said high performance polyethylene fibers (HPPE) have a toughness of at least 1.5 N / tex up to a maximum of 6 N / tex.
    [2]
    2. High strength fiber according to claim 1, characterized in that the degree of crosslinking of the crosslinked silicone polymer is at least 30%.
    [3]
    3. High strength fiber according to claim 1 or 2, characterized by the fact that the fiber is made of ultrahigh molecular weight polyethylene (UHMWPE) with an intrinsic viscosity of at least 5 dl / g determined in 135 ° decaline Ç.
    [4]
    4. Cable comprising high strength fibers, preferably including HPPE fibers as defined in claim 1, characterized in that the cable is provided with a coating comprising a crosslinked silicone polymer, and in which the degree of crosslinking of the polymer cross-linked silicone is at least 20%, preferably at least 30%, and in which said high-performance polyethylene (HPPE) fibers have a toughness of at least 1.5 N / tex up to a maximum of 6 N / tex.
    [5]
    5. Filament comprising high strength fibers, preferably including HPPE fibers, as defined in claim 1, characterized by the fact that the
    Petition 870190033715, of 4/8/2019, p. 8/10
    2/3 filament is provided with a coating comprising a crosslinked silicone polymer, and in which the degree of crosslinking of the crosslinked silicone polymer is at least 20%, preferably at least 30%, and in which said polyethylene fibers of high performance (HPPE) have a toughness of at least 1.5 N / tex up to a maximum of 6 N / tex.
    [6]
    6. Method for manufacturing high-strength coated fibers, as defined in claim 1, characterized by the fact that it comprises the steps of:
    a) applying a coating composition comprising a silicone polymer crosslinkable to high strength fibers;
    b) crosslinking of the silicone polymer, and in which the degree of crosslinking of the crosslinked silicone polymer is at least 20%, preferably at least 30% and
    said fibers of polyethylene in high performance (HPPE) have a tenacity of at least 1.5 N / tex up until at the maximum7. 6 N / tex.Method, according with The claim 6,
    characterized by the fact that the crosslinkable silicone polymer comprises a silicone polymer having a crosslinkable end group.
    [7]
    8. Method according to claim 7, characterized in that the crosslinkable end group is a vinyl group.
    [8]
    Method according to any one of claims 6 to 8, characterized in that the crosslinkable silicone polymer comprises the following formula:
    CH2 = CH- (Si (CH3) 2O) n-CH = CH2 (1)
    Petition 870190033715, of 4/8/2019, p. 9/10
    3/3 where n is a number from 2 to 200.
    [9]
    Method according to any one of claims 6 to 9, characterized in that the crosslinkable silicone polymer comprises the following formula:
    Si (CH3) 3 O- (SiCH3HO) m-Si (CH3) 3 (2) where m is a number from 2 to 200.
    [10]
    Method according to any one of claims 7 to 10, characterized in that the coating composition additionally comprises a platinum catalyst.
    [11]
    12. Method of making a cable comprising high strength fibers, characterized by the fact that it comprises the steps of:
    a) preparing high performance polyethylene fibers (HPPE) according to the method defined in claim 6, and wherein said high performance polyethylene fibers (HPPE) have a toughness of at least 1.5 N / tex up to a maximum of 6 N / tex.
    b) construction of a cable from coated fibers obtained in step a).
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    同族专利:
    公开号 | 公开日
    DK2462275T3|2016-09-26|
    JP5664982B2|2015-02-04|
    AU2010280899B2|2016-02-18|
    US20120198808A1|2012-08-09|
    KR101758939B1|2017-07-17|
    KR20120041239A|2012-04-30|
    LT2462275T|2016-10-10|
    CN106948177A|2017-07-14|
    CA2769497A1|2011-02-10|
    EA201200240A1|2012-07-30|
    CN102471997A|2012-05-23|
    ZA201200374B|2013-06-26|
    IN2012DN00577A|2015-06-12|
    CA2769497C|2017-11-28|
    EA021519B1|2015-07-30|
    WO2011015485A1|2011-02-10|
    PE20121271A1|2012-10-07|
    EP2462275B1|2016-06-29|
    SI2462275T1|2016-10-28|
    PT2462275T|2016-08-26|
    JP2013501161A|2013-01-10|
    CL2012000259A1|2012-07-06|
    AU2010280899A1|2012-02-09|
    BR112012002556A2|2016-03-15|
    SG177661A1|2012-03-29|
    EP2462275A1|2012-06-13|
    US8881496B2|2014-11-11|
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    法律状态:
    2019-02-05| B06T| Formal requirements before examination|
    2019-11-05| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/07/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09167161|2009-08-04|
    PCT/EP2010/060813|WO2011015485A1|2009-08-04|2010-07-26|Coated high strength fibers|
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