CN106555247A - A kind of cut resistant superhigh molecular weight polyethylene fibers and its preparation method and application - Google Patents

A kind of cut resistant superhigh molecular weight polyethylene fibers and its preparation method and application Download PDF

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Publication number
CN106555247A
CN106555247A CN201510617006.8A CN201510617006A CN106555247A CN 106555247 A CN106555247 A CN 106555247A CN 201510617006 A CN201510617006 A CN 201510617006A CN 106555247 A CN106555247 A CN 106555247A
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molecular weight
weight polyethylene
polyethylene fibers
superhigh molecular
cut resistant
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CN106555247B (en
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贺鹏
黄兴良
刘晓徽
吴璇
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Beijing Tongyizhong Specialty Fiber Technology & Development Co Ltd
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Beijing Tongyizhong Specialty Fiber Technology & Development Co Ltd
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00Treatment of filament-forming or like material
    • D01D1/02Preparation of spinning solutions
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention provides a kind of cut resistant superhigh molecular weight polyethylene fibers and its preparation method and application, the cut resistant superhigh molecular weight polyethylene fibers include:Superhigh molecular weight polyethylene fibers;The hard fibre being dispersed in the superhigh molecular weight polyethylene fibers and iron powder;The mass ratio of the superhigh molecular weight polyethylene fibers, hard fibre and iron powder is 100:(3~6):(0.01~0.05).Compared with prior art, the cut resistant superhigh molecular weight polyethylene fibers that the present invention is provided are interacted with hard fibre by iron powder, it is possible to increase the intensity of finished fiber on the basis of belt cutting-resisting property EN388 Pyatyi standards are met;Meanwhile, the addition of iron powder is conducive to hard fibre being uniformly distributed in ultra-high molecular weight polyethylene, makes finished fiber have relatively low change rate of strength, improves the quality stability of finished fiber.

Description

A kind of cut resistant superhigh molecular weight polyethylene fibers and its preparation method and application
Technical field
The present invention relates to superhigh molecular weight polyethylene fibers technical field, more specifically, is to be related to one kind Cut resistant superhigh molecular weight polyethylene fibers and its preparation method and application.
Background technology
Superhigh molecular weight polyethylene fibers, also known as high-strength high-modulus polyethylene fiber, refer to by relative molecular weight The spun next fiber of polyethylene more than 1,000,000.As superhigh molecular weight polyethylene fibers have quality Gently, impact resistance, the advantages of dielectric properties are high, be widely used in aerospace field, marine site defence field, Weaponry field and daily industrial circle.
In daily industrial circle, superhigh molecular weight polyethylene fibers are most commonly employed to prepare with cut resistant work( The product of energy, for example, cut resistant gloves, cut resistant tent, cut resistant rope etc..But, only by gathering The belt cutting-resisting property of superhigh molecular weight polyethylene fibers prepared by ethylene powder is limited, the industry being made from it The belt cutting-resisting property of glove is only capable of reaching the three-level of industrial gloves protection European standard EN388 standard and requires;And By being added to glass fibre, require can the Pyatyi that belt cutting-resisting property reaches EN388 standards, but As the pliability and comfortableness of glass fibre are poor, practical application is unsatisfactory.Therefore, answer actual Use it is more point to exploitation it is a kind of can reach the requirement of EN388 Pyatyis, while and the superelevation of soft comfortable point Sub- weight polyethylene fiber, for preparing the products such as industrial gloves.
At present, people are by improving the many-sides such as dispensing, the spinning technique of superhigh molecular weight polyethylene fibers Improve the belt cutting-resisting property of finished fiber.Patent documentation US5976998 discloses a kind of filled cut-resistant fiber, Hard filler of the fiber by fibre-forming polymer and Moh's scale number more than 3 is made.But, due to what is used The granularity of hard filler is little, consumption is few, and hard filler is difficult in superhigh molecular weight polyethylene fibers Net distribution, therefore the cutting resistance of superhigh molecular weight polyethylene fibers that the method is obtained do not had The improvement of effect.
Patent documentation WO2008046476 discloses a kind of cut resistant yarn, and which includes silk thread and/or fixed length The hard component of fiber, described silk thread and/or staple fibre comprising the cutting resistance for being used to improve yarn, Wherein described hard component is many hard fibres that average diameter is 25 μm to the maximum.Although the method is obtained The cutting resistance of superhigh molecular weight polyethylene fibers be effectively improved, but, due to hard component With less particle diameter and larger specific surface area, hard component inherently easily occurs to reunite, and due to Spinning liquid has viscosity, is difficult to be uniformly dispersed when hard component is mixed with spinning liquid, causes finished product Fibre strength is affected and quality stability is poor, and the change rate of strength for showing as finished fiber is high.
The content of the invention
In view of this, it is an object of the invention to provide a kind of cut resistant superhigh molecular weight polyethylene fibers and Its preparation method and application, the cut resistant superhigh molecular weight polyethylene fibers fibre strength that the present invention is provided are high And change rate of strength is low.
The invention provides a kind of cut resistant superhigh molecular weight polyethylene fibers, including:
Superhigh molecular weight polyethylene fibers;
The hard fibre being dispersed in the superhigh molecular weight polyethylene fibers and iron powder;
The mass ratio of the superhigh molecular weight polyethylene fibers, hard fibre and iron powder is 100:(3~6): (0.01~0.05).
Preferably, the weight average molecular weight of the superhigh molecular weight polyethylene fibers is 3.0 × 106~5 × 106, Molecular weight distribution≤9.0.
Preferably, the hard fibre include one kind in ceramic fibre, carbon fiber and silicon carbide whisker or It is various.
Preferably, the average diameter of the hard fibre is less than or equal to 9 μm more than 0, and draw ratio is more than 0 Less than or equal to 30.
Preferably, the mean diameter of the iron powder is 10 μm~44 μm.
Present invention also offers the cut resistant superhigh molecular weight polyethylene fibers described in a kind of above-mentioned technical proposal Preparation method, comprise the following steps:
A) hard fibre, iron powder and solvent naphtha are mixed, obtains mixed liquor A;
B) mixed liquor A is mixed with ultra-high molecular weight polyethylene lysate, obtains spinning solution;
C) spinning solution is carried out successively spinning, preliminary draft, extraction, drying and positive drawing-off, obtain Cut resistant superhigh molecular weight polyethylene fibers.
Preferably, solvent naphtha described in step a) by 70%~95% the cycloalkanes containing 25~50 carbon atoms Hydrocarbon and 5%~30% containing 25~50 carbon atoms chain hydrocarbon composition.
Preferably, the mass ratio of hard fibre, iron powder and solvent naphtha described in step a) is (3~6): (0.01~0.05):(10~24).
Preferably, described in step b), ultra-high molecular weight polyethylene lysate includes:
100 weight portion of ultra-high molecular weight polyethylene;
800 weight portion~2800 weight portion of solvent naphtha.
Present invention also offers the cut resistant superhigh molecular weight polyethylene fibers described in a kind of above-mentioned technical proposal As the application of cut resistant material.
The invention provides a kind of cut resistant superhigh molecular weight polyethylene fibers and its preparation method and application, The cut resistant superhigh molecular weight polyethylene fibers include:Superhigh molecular weight polyethylene fibers;It is dispersed in institute State the hard fibre and iron powder in superhigh molecular weight polyethylene fibers;The superhigh molecular weight polyethylene fibers, The mass ratio of hard fibre and iron powder is 100:(3~6):(0.01~0.05).Compared with prior art, The cut resistant superhigh molecular weight polyethylene fibers that the present invention is provided are meeting belt cutting-resisting property EN388 Pyatyi marks On the basis of standard, interacted with hard fibre by iron powder, it is possible to increase the intensity of finished fiber;Together When, the addition of iron powder is conducive to hard fibre being uniformly distributed in ultra-high molecular weight polyethylene, makes finished product Fiber has relatively low change rate of strength, improves the quality stability of finished fiber.Test result indicate that, The fibre strength of the cut resistant superhigh molecular weight polyethylene fibers that the present invention is provided can reach 26.9cN/dtex, change rate of strength are less than 5.0%.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, Obviously, described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole. Based on the embodiment in the present invention, those of ordinary skill in the art are not under the premise of creative work is made The every other embodiment for being obtained, belongs to the scope of protection of the invention.
The invention provides a kind of cut resistant superhigh molecular weight polyethylene fibers, including:
Superhigh molecular weight polyethylene fibers;
The hard fibre being dispersed in the superhigh molecular weight polyethylene fibers and iron powder;
The mass ratio of the superhigh molecular weight polyethylene fibers, hard fibre and iron powder is 100:(3~6): (0.01~0.05).
In the present invention, the weight average molecular weight of the superhigh molecular weight polyethylene fibers is preferably 3.0 × 106~5 ×106, more preferably 3.5 × 106~4.5 × 106;The molecular weight of the superhigh molecular weight polyethylene fibers point Cloth is preferably≤9.0, more preferably 5.0.In the present invention, the superhigh molecular weight polyethylene fibers are described The matrix of cut resistant superhigh molecular weight polyethylene fibers, with higher structural regularity and consistency, from And make the product integrally mechanical property with high-strength and high-modulus amount.
In the present invention, the hard fibre is preferably included in ceramic fibre, carbon fiber and silicon carbide whisker One or more, the more preferably mixture of ceramic fibre, carbon fiber and silicon carbide whisker.At this In bright, the hard fibre is the reinforcing material of the cut resistant superhigh molecular weight polyethylene fibers, can The intensity of finished fiber is effectively improved, product belt cutting-resisting property is improved;The present invention is to the hard fibre Source is not particularly limited, using above-mentioned ceramic fibre well known to those skilled in the art, carbon fiber and carbon The commercial goods of SiClx whisker.In the present invention, the ceramic fibre, carbon fiber and silicon carbide whisker In the mixture of palpus, the mass ratio of ceramic fibre, carbon fiber and silicon carbide whisker is preferably 1:(7~8.8): (0.2~1), more preferably 1:(7.3~8.4):(0.25~0.8), most preferably 1:(7.5~8): (0.3~0.5).In the present invention, the average diameter of the hard fibre preferably greater than 0 is less than or equal to 9 μm, more preferably greater than 0 is less than or equal to 7 μm;The draw ratio of the hard fibre preferably greater than 0 is less than 20 are less than or equal to equal to 30, more preferably greater than 0.
In the present invention, the iron powder can be interacted with the hard fibre, improve finished fiber strong While spending, be conducive to hard fibre being uniformly distributed in ultra-high molecular weight polyethylene;The present invention is to institute The source for stating iron powder is not particularly limited, using commercial goods well known to those skilled in the art. In the present invention, the mean diameter of the iron powder is preferably 10 μm~44 μm, and more preferably 20 μm~30 μm。
In the present invention, the mass ratio of the superhigh molecular weight polyethylene fibers, hard fibre and iron powder is 100:(3~6):(0.01~0.05), preferably 100:(4~5):(0.02~0.04).
Present invention also offers the cut resistant superhigh molecular weight polyethylene fibers described in a kind of above-mentioned technical proposal Preparation method, comprise the following steps:
A) hard fibre, iron powder and solvent naphtha are mixed, obtains mixed liquor A;
B) mixed liquor A is mixed with ultra-high molecular weight polyethylene lysate, obtains spinning solution;
C) spinning solution is carried out successively spinning, preliminary draft, extraction, drying and positive drawing-off, obtain Cut resistant superhigh molecular weight polyethylene fibers.
In the present invention, hard fibre, iron powder and solvent naphtha are mixed, obtains mixed liquor A.At this In bright, the hard fibre preferably includes one kind in ceramic fibre, carbon fiber and silicon carbide whisker or many Plant, more preferably the mixture of ceramic fibre, carbon fiber and silicon carbide whisker.In the present invention, it is described Hard fibre is the reinforcing material of the cut resistant superhigh molecular weight polyethylene fibers, can be effectively improved into The intensity of product fiber, improves product belt cutting-resisting property;The present invention does not have spy to the source of the hard fibre It is different to limit, using above-mentioned ceramic fibre well known to those skilled in the art, carbon fiber and silicon carbide whisker Commercial goods.In the present invention, the mixture of the ceramic fibre, carbon fiber and silicon carbide whisker The mass ratio of middle ceramic fibre, carbon fiber and silicon carbide whisker is preferably 1:(7~8.8):(0.2~1), More preferably 1:(7.3~8.4):(0.25~0.8), most preferably 1:(7.5~8):(0.3~0.5). In the present invention, the average diameter of the hard fibre is preferably greater than 0 and is less than or equal to 9 μm, more preferably It is to be less than or equal to 7 μm more than 0;The draw ratio of the hard fibre is preferably greater than 0 and is less than or equal to 30, More preferably higher than 0 is less than or equal to 20.
In the present invention, the iron powder can be interacted with the hard fibre, improve finished fiber strong While spending, be conducive to hard fibre being uniformly distributed in ultra-high molecular weight polyethylene;The present invention is to institute The source for stating iron powder is not particularly limited, using commercial goods well known to those skilled in the art. In the present invention, the mean diameter of the iron powder is preferably 10 μm~44 μm, and more preferably 20 μm~30 μm。
In the present invention, the solvent naphtha preferably by 70%~95% the cycloalkane containing 25~50 carbon atoms With 5%~30% composition of the chain hydrocarbon containing 25~50 carbon atoms, more preferably by 85%~90% containing 25~50 The cycloalkane of individual carbon atom and 10%~15% containing 25~50 carbon atoms chain hydrocarbon composition, most preferably in vain Oil.In the present invention, the kinematic viscosity of the solvent naphtha is preferably 61.2mm2/ s~74.8mm2/s;This The bright source to the solvent naphtha is not particularly limited, using 5# white oils well known to those skilled in the art, 7# white oils, 10# white oils, 15# white oils, 22# white oils, 26# white oils, 32# white oils, 46# white oils, 68# are white The commercial goods of oil, 70# white oils, 100# white oils and 150# white oils.In the present invention, the solvent Hard fibre and iron powder are uniformly divided by solvent of the oil for ultra-high molecular weight polyethylene lysate, the present invention first It is dispersed in solvent naphtha, is conducive to hard fibre and iron powder further in superhigh molecular weight polyethylene fibers Dispersion.
In the present invention, after by the mixing of hard fibre, iron powder and solvent naphtha, the mixed solution A for obtaining Kinematic viscosity can change according to the addition of hard fibre and iron powder, have shadow to the mechanical property of product Ring, addition is too high, the kinematic viscosity of mixed solution A is reduced, product broken end number increase can be made, added Amount is too low, is unfavorable for the raising of fibre strength, makes the cutting resistance and intensity decreases of product.In the present invention In, hard fibre, iron powder and solvent naphtha are mixed;The quality of the hard fibre, iron powder and solvent naphtha Than being preferably (3~6):(0.01~0.05):(10~24), more preferably (4~5):(0.02~0.04): (14~20).
In the present invention, the process of the mixing is preferably specially:
Hard fibre, iron powder and solvent naphtha are mixed under conditions of stirring.The present invention is stirred to described The method mixed is not particularly limited, equal using manual stirring well known to those skilled in the art or mechanical agitation Can.In the present invention, the speed of the stirring is preferably 1000rpm~4500rpm, more preferably 2000rpm~3000rpm;The present invention was not particularly limited to the time stirred, and made hard fibre and iron powder exist It is uniformly dispersed in solvent naphtha.
After obtaining the mixed liquor A, the mixed liquor A is dissolved by the present invention with ultra-high molecular weight polyethylene Liquid mixes, and obtains spinning solution.In the present invention, the ultra-high molecular weight polyethylene lysate is preferably wrapped Include:
100 weight portion of ultra-high molecular weight polyethylene;
800 weight portion~2800 weight portion of solvent naphtha.
In the present invention, the ultra-high molecular weight polyethylene by ultra-high molecular weight polyethylene powder described molten Obtain after dissolving in agent oil;The present invention does not have special limit to the source of the ultra-high molecular weight polyethylene powder System, using commercial goods well known to those skilled in the art.In the present invention, the supra polymer The weight average molecular weight of weight northylen powder is preferably 3.0 × 106~5 × 106, more preferably 3.5 × 106~4.5 ×106;The molecular weight distribution of the ultra-high molecular weight polyethylene powder is preferably≤9.0, more preferably 5.0; The particle diameter of the ultra-high molecular weight polyethylene powder is preferably 40 mesh~100 mesh, more preferably 60 mesh~80 Mesh.In the present invention, the ultra-high molecular weight polyethylene lysate preferably includes ultra-high molecular weight polyethylene 100 weight portions.
In the present invention, the solvent naphtha preferably by 70%~95% the cycloalkane containing 25~50 carbon atoms With 5%~30% composition of the chain hydrocarbon containing 25~50 carbon atoms, more preferably by 85%~90% containing 25~50 The cycloalkane of individual carbon atom and 10%~15% containing 25~50 carbon atoms chain hydrocarbon composition, most preferably in vain Oil.In the present invention, the initial boiling point of the solvent naphtha is higher than 450 DEG C;The kinematic viscosity of the solvent naphtha is excellent Elect 61.2mm as2/ s~74.8mm2/s;The present invention is not particularly limited to the source of the solvent naphtha, is adopted 5# white oils well known to those skilled in the art, 7# white oils, 10# white oils, 15# white oils, 22# white oils, 26# White oil, 32# white oils, 46# white oils, 68# white oils, 70# white oils, 100# white oils and 150# white oils it is commercially available Commodity.In the present invention, the solvent naphtha in the ultra-high molecular weight polyethylene lysate is mixed with described The solvent naphtha closed in solution A is preferably identical solvent naphtha, is conducive to the ultra-high molecular weight polyethylene molten Solution liquid is miscible with the mixed solution A.In the present invention, the ultra-high molecular weight polyethylene lysate Preferably include 800 weight portion~2800 weight portion of solvent naphtha, more preferably 1100 weight portion~2000 weight Part.
In the present invention, the preparation method of the ultra-high molecular weight polyethylene lysate is preferably specially:
Ultra-high molecular weight polyethylene powder is mixed with solvent naphtha, ultra-high molecular weight polyethylene lysate is obtained. In the present invention, it is described that the process that ultra-high molecular weight polyethylene powder is mixed with solvent naphtha is preferably specially:
Ultra-high molecular weight polyethylene powder is added in solvent naphtha, is stirred, obtain super high molecular weight Polyethylene lysate.The present invention is not particularly limited to the method for the stirring, using people in the art Manual stirring or mechanical agitation known to member.In the present invention, the speed of the stirring is preferably 30rpm~500rpm, more preferably 60rpm~100rpm;The temperature of the stirring is preferably 80 DEG C~120 DEG C, more preferably 100 DEG C~110 DEG C;The time of the stirring is preferably 0.5h~5h, more preferably 1h~2h.
In the present invention, the mixed liquor A is mixed with ultra-high molecular weight polyethylene lysate, is spun Silk stock solution.In the present invention, the mistake that mixed liquor A is mixed with ultra-high molecular weight polyethylene lysate Cheng Youxuan is specially:
Mixed liquor A is added in ultra-high molecular weight polyethylene lysate, is stirred, obtain spinning former Liquid.The present invention is not particularly limited to the method for the stirring, using people well known to those skilled in the art Work is stirred or mechanical agitation.In the present invention, the speed of the stirring is preferably 60rpm~100rpm, More preferably 80rpm~90rpm;The temperature of the stirring is preferably 100 DEG C~160 DEG C, and more preferably 120 DEG C~140 DEG C;The time of the stirring is preferably 1h~6h, more preferably 2h~3h.
After obtaining spinning solution, the spinning solution is carried out spinning by the present invention successively, preliminary draft, extraction, It is dried and positive drawing-off, obtains cut resistant superhigh molecular weight polyethylene fibers.In the present invention, it is spinning is former Liquid is spinned, and obtains gel fiber.In the present invention, the process of the spinning is preferably specially:
The spinning solution is carried out successively filter, spray webbing and cooling, obtain gel fiber.In the present invention, The spinning solution is filtered.The present invention is not particularly limited to the equipment of the filtration, is preferably adopted Use filter;The aperture of the filter is preferably 30 mesh~100 mesh, more preferably 60 mesh~70 mesh.
After completing the filter process, the spinning solution after filtration is carried out spray webbing and cooling by the present invention, is obtained To gel fiber.In the present invention, the equipment of the spray webbing is preferably manifold, and the present invention does not have spy to this It is different to limit;The product that the present invention will be obtained Jing after manifold spray webbing, is directly cooled down, is obtained gel fiber. The present invention is not particularly limited to the method for the cooling, it is preferred to use water well known to those skilled in the art The technical scheme of bath cooling;The temperature of the water-bath cooling is preferably 20 DEG C~30 DEG C, more preferably 22 DEG C ~25 DEG C.
After completing the spinning process, the gel fiber obtained after spinning is carried out preliminary draft by the present invention.At this In invention, the preliminary draft can reduce the internal stress of gel fiber internal residual.In the present invention, it is described The draft ratio of preliminary draft is preferably 1~10 times, more preferably 3~5 times;The temperature of the preliminary draft is preferred For 20 DEG C~30 DEG C, more preferably 25 DEG C.
After completing the preliminary draft process, the gel fiber after preliminary draft is extracted and is dried by the present invention. In the present invention, the purpose of the extraction is to remove the solvent naphtha in gel fiber.In the present invention, it is described Extractant used by extraction process is preferably in white oil extractant, normal hexane, gasoline and tetrahydro carbon Plant or various.In the present invention, the extractant has good intermiscibility to solvent naphtha, and the present invention is right The source of the extractant is not particularly limited, and is extracted using above-mentioned white oil well known to those skilled in the art The commercial goods of agent, normal hexane, gasoline and tetrahydro carbon.In the present invention, the mesh of the drying Be to make extractant volatilize.In the present invention, the temperature of the drying is preferably 25 DEG C~45 DEG C, more preferably For 30 DEG C~40 DEG C.
After completing the extraction and dry run, extraction and dried gel fiber are just led by the present invention Stretch, obtain cut resistant superhigh molecular weight polyethylene fibers.In the present invention, the temperature of the positive drawing-off is excellent Elect 120 DEG C~160 DEG C as, more preferably 140 DEG C~150 DEG C;The draft ratio of the positive drawing-off is preferably 4~20 times, more preferably 6~10 times.In the present invention, the positive drawing-off can make fiber deform, Finished fiber is obtained, the fibre deformation speed is had a major impact to the mechanical property of product, such as fruit fiber Deformation velocity it is too fast, then there is fracture, and the deformation of fiber in fiber before enough draft ratios are reached Speed is excessively slow, then in drawing process, strand relaxes, and cannot get high strength fibre.In the present invention, The deformation velocity of the fiber is preferably 0.005s-1~0.5s-1, more preferably 0.01s-1~0.1s-1
Present invention also offers the cut resistant superhigh molecular weight polyethylene fibers described in a kind of above-mentioned technical proposal As the application of cut resistant material.In the present invention, the cut resistant material is with cut resistant function Product, preferably cut resistant yarn.The present invention does not have special limit to the preparation method of the cut resistant yarn System, the method processed using yarn well known to those skilled in the art.In the present invention, it is described resistance to Chopped strands can obtain different types of cut resistant product by knitting or braiding, such as cut resistant gloves, Cut resistant tent, cut resistant rope etc..
The invention provides a kind of cut resistant superhigh molecular weight polyethylene fibers and its preparation method and application, The cut resistant superhigh molecular weight polyethylene fibers include:Superhigh molecular weight polyethylene fibers;It is dispersed in institute State the hard fibre and iron powder in superhigh molecular weight polyethylene fibers;The superhigh molecular weight polyethylene fibers, The mass ratio of hard fibre and iron powder is 100:(3~6):(0.01~0.05).Compared with prior art, The cut resistant superhigh molecular weight polyethylene fibers that the present invention is provided are meeting belt cutting-resisting property EN388 Pyatyi marks On the basis of standard, interacted with hard fibre by iron powder, it is possible to increase the intensity of finished fiber;Together When, the addition of iron powder is conducive to hard fibre being uniformly distributed in ultra-high molecular weight polyethylene, makes finished product Fiber has relatively low change rate of strength, improves the quality stability of finished fiber.Test result indicate that, The fibre strength of the cut resistant superhigh molecular weight polyethylene fibers that the present invention is provided can reach 26.9cN/dtex, change rate of strength are less than 3.0%.
Additionally, the uniformity of the cut resistant superhigh molecular weight polyethylene fibers of present invention offer is preferably, quality Stability is high, and obtained industrial gloves belt cutting-resisting property is excellent.
In order to further illustrate the present invention, it is described in detail below by following examples.The present invention with Ultra-high molecular weight polyethylene powder used by lower embodiment is provided by Yanshan Petrochemical;Ceramic fibre used is by mountain Eastern Luyang limited company provides, and the average diameter of the ceramic fibre is less than or equal to 9 μm, draw ratio Less than or equal to 30;Carbon fiber used multiple Condor carbon fiber company limited by provides, the carbon fiber it is flat Diameter is less than or equal to 9 μm, and draw ratio is less than or equal to 30;Silicon carbide whisker used is high by one promise of Qinhuangdao New material development corporation, Ltd. provides, and the average diameter of the silicon carbide whisker is less than or equal to 9 μm, major diameter Than less than or equal to 30;Iron powder used is provided by Shandong Hong Fa iron powders trade Co., Ltd, the iron powder it is flat Particle diameter is 10 μm~44 μm;White oil used is provided by Total SA;White oil extractant used is by upper Hai Xile Chemical Co., Ltd.s provide.
Embodiment 1
(1) 50g ceramic fibres, 375g carbon fibers, 25g silicon carbide whiskers and 3g iron powders are added into 1.8kg In 68# white oils, it is stirred until homogeneous under 2500rpm, obtains mixed liquor A.
(2) by 10kg weight average molecular weight be 4.2 × 106, the super high molecular weight that molecular weight distribution is 5.0 During polyethylene powders add 160kg 68# white oils, 1.5h is stirred at 80rpm, 105 DEG C, obtain superelevation Molecular weight polyethylene lysate;Addition step (1) in the ultra-high molecular weight polyethylene lysate again The mixed liquor A for obtaining, at 85rpm, 130 DEG C stirs 2.5h, obtains spinning solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then Jing after manifold spray webbing, is produced Thing water-bath cooling at 25 DEG C, obtains gel fiber;Then the gel fiber is existed with 4 times of draft ratio Preliminary draft is carried out at 25 DEG C, then Jing after the extraction of white oil extractant, is dried at 40 DEG C, finally at 145 DEG C Under positive drawing-off is carried out with 7 times of draft ratio, control fiber deformation velocity be 0.020s-1, obtain resistance to cutting Cut superhigh molecular weight polyethylene fibers.
Embodiment 2
(1) 50g ceramic fibres, 385g carbon fibers, 15g silicon carbide whiskers and 2g iron powders are added into 1.4kg In 68# white oils, it is stirred until homogeneous under 2000rpm, obtains mixed liquor A.
(2) by 10kg weight average molecular weight be 3.5 × 106, the super high molecular weight that molecular weight distribution is 5.0 During polyethylene powders add 110kg 68# white oils, 2h is stirred at 60rpm, 100 DEG C, obtain superelevation point Sub- weight northylen lysate;In the ultra-high molecular weight polyethylene lysate step (1) is added to obtain again The mixed liquor A for arriving, at 80rpm, 120 DEG C stirs 3h, obtains spinning solution.
(3) filter that spinning solution via hole diameter is 70 mesh is filtered, then Jing after manifold spray webbing, is produced Thing water-bath cooling at 22 DEG C, obtains gel fiber;Then the gel fiber is existed with 5 times of draft ratio Preliminary draft is carried out at 25 DEG C, then Jing after the extraction of white oil extractant, is dried at 40 DEG C, finally at 140 DEG C Under positive drawing-off is carried out with 6 times of draft ratio, control fiber deformation velocity be 0.025s-1, obtain resistance to cutting Cut superhigh molecular weight polyethylene fibers.
Embodiment 3
(1) 56g ceramic fibres, 417g carbon fibers, 28g silicon carbide whiskers and 4g iron powders are added into 2.0kg In 68# white oils, it is stirred until homogeneous at 3,000 rpm, obtains mixed liquor A.
(2) by 10kg weight average molecular weight be 4.5 × 106, the super high molecular weight that molecular weight distribution is 5.0 During polyethylene powders add 200kg 68# white oils, 1h is stirred at 100rpm, 110 DEG C, obtain superelevation Molecular weight polyethylene lysate;Addition step (1) in the ultra-high molecular weight polyethylene lysate again The mixed liquor A for obtaining, at 90rpm, 140 DEG C stirs 2h, obtains spinning solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then Jing after manifold spray webbing, is produced Thing water-bath cooling at 25 DEG C, obtains gel fiber;Then the gel fiber is existed with 3 times of draft ratio Preliminary draft is carried out at 25 DEG C, then Jing after the extraction of white oil extractant, is dried at 40 DEG C, finally at 150 DEG C Under positive drawing-off is carried out with 8 times of draft ratio, control fiber deformation velocity be 0.0118s-1, obtain resistance to Cutting superhigh molecular weight polyethylene fibers.
Embodiment 4
(1) 450g ceramic fibres and 3g iron powders are added in 1.8kg 68# white oils, under 2500rpm It is stirred until homogeneous, obtains mixed liquor A.
(2) by 10kg weight average molecular weight be 4.2 × 106, the super high molecular weight that molecular weight distribution is 5.0 During polyethylene powders add 160kg 68# white oils, 1.5h is stirred at 80rpm, 105 DEG C, obtain superelevation Molecular weight polyethylene lysate;Addition step (1) in the ultra-high molecular weight polyethylene lysate again The mixed liquor A for obtaining, at 85rpm, 130 DEG C stirs 2.5h, obtains spinning solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then Jing after manifold spray webbing, is produced Thing water-bath cooling at 25 DEG C, obtains gel fiber;Then the gel fiber is existed with 4 times of draft ratio Preliminary draft is carried out at 25 DEG C, then Jing after the extraction of white oil extractant, is dried at 30 DEG C, finally at 145 DEG C Under positive drawing-off is carried out with 7 times of draft ratio, control fiber deformation velocity be 0.020s-1, obtain resistance to cutting Cut superhigh molecular weight polyethylene fibers.
Embodiment 5
(1) 450g carbon fibers and 3g iron powders are added in 1.8kg 68# white oils, is stirred under 2500rpm Mix to uniform, obtain mixed liquor A.
(2) by 10kg weight average molecular weight be 4.2 × 106, the super high molecular weight that molecular weight distribution is 5.0 During polyethylene powders add 160kg 68# white oils, 1.5h is stirred at 80rpm, 105 DEG C, obtain superelevation Molecular weight polyethylene lysate;Addition step (1) in the ultra-high molecular weight polyethylene lysate again The mixed liquor A for obtaining, at 85rpm, 130 DEG C stirs 2.5h, obtains spinning solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then Jing after manifold spray webbing, is produced Thing water-bath cooling at 25 DEG C, obtains gel fiber;Then the gel fiber is existed with 4 times of draft ratio Preliminary draft is carried out at 25 DEG C, then Jing after the extraction of white oil extractant, is dried at 30 DEG C, finally at 145 DEG C Under positive drawing-off is carried out with 7 times of draft ratio, control fiber deformation velocity be 0.020s-1, obtain resistance to cutting Cut superhigh molecular weight polyethylene fibers.
Embodiment 6
(1) 450g silicon carbide whiskers and 3g iron powders are added in 1.8kg 68# white oils, in 2500rpm Under be stirred until homogeneous, obtain mixed liquor A.
(2) by 10kg weight average molecular weight be 4.2 × 106, the super high molecular weight that molecular weight distribution is 5.0 During polyethylene powders add 160kg 68# white oils, 1.5h is stirred at 80rpm, 105 DEG C, obtain superelevation Molecular weight polyethylene lysate;Addition step (1) in the ultra-high molecular weight polyethylene lysate again The mixed liquor A for obtaining, at 85rpm, 130 DEG C stirs 2.5h, obtains spinning solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then Jing after manifold spray webbing, is produced Thing water-bath cooling at 25 DEG C, obtains gel fiber;Then the gel fiber is existed with 4 times of draft ratio Preliminary draft is carried out at 25 DEG C, then Jing after the extraction of white oil extractant, is dried at 30 DEG C, finally at 145 DEG C Under positive drawing-off is carried out with 7 times of draft ratio, control fiber deformation velocity be 0.020s-1, obtain resistance to cutting Cut superhigh molecular weight polyethylene fibers.
Using DXLL-20000 electronic tensile machines according to specified in GBT 19975-2005 method to reality Fibre strength, modulus and the extension at break of the cut resistant superhigh molecular weight polyethylene fibers of the offer of example 1~6 are provided Rate is tested, the cut resistant superelevation point provided to embodiment 1~6 using YG086 types measuring reel The fiber number of sub- weight polyethylene fiber is tested, and the number that breaks end, the broken end number are obtained during silk is connect It is expressed as the every myriametre broken end number of finished fiber.Test result is as shown in table 1.
The fibre strength data of the cut resistant superhigh molecular weight polyethylene fibers that 1 embodiment of table 1~6 is provided
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Intensity (cN/dtex) 26.9 26.5 26.8 25.8 26.1 26.3
Modulus (cN/dtex) 998 951 987 880 936 943
Fiber number (denier) 397.5 374 445.5 418 401.5 412.5
Elongation at break (%) 3.4 4.6 4.1 3.9 4.8 4.2
Broken end number (individual/myriametre) 0.5 1.5 1.1 0.8 1.0 1.2
Cut resistant superhigh molecular weight polyethylene fibers embodiment 1~6 provided using Instron types puller system Change rate of strength tested, while using YG086 types measuring reel to embodiment 1~6 provide The cut resistant superhigh molecular weight polyethylene fibers difference substantial amounts of fiber number data of follow-on test, then by side Difference calculates fiber number coefficient of variation CV value, and test result is as shown in table 2.
The change rate of strength data of the cut resistant superhigh molecular weight polyethylene fibers that 2 embodiment of table 1~6 is provided
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Change rate of strength 3.0% 4.2% 3.8% 4.7% 4.3% 5.0%
Fiber number coefficient of variation CV 0.1% 1.1% 0.7% 1.5% 0.8% 0.2%
Test result shows that the cut resistant superhigh molecular weight polyethylene fibers that the embodiment of the present invention 1~6 is provided have There is higher fibre strength, while the change rate of strength of finished fiber is relatively low, i.e., strength stability is good;This Outward, product fiber number coefficient of variation CV is relatively low, while product elongation at break is stable, broken end number is relatively low, from And ensure that product has preferable uniformity and quality stability.
The cut resistant superhigh molecular weight polyethylene fibers that Example 1~6 is provided, respectively along bobbin by positive and negative Direction winds, and makes the cut resistant yarn of 400D, then above-mentioned cut resistant yarn is carried out coating, woven, Respectively obtain cut resistant industrial gloves.European standard EN388 standard, opponent is protected to pack into according to industrial gloves Row anti-cut performance test, measurement wear out number of times, take two samples every time, measure five times, according to coefficient Calculate meansigma methodss.Test result is as shown in table 3.
The cut resistant superhigh molecular weight polyethylene fibers belt cutting-resisting property data that 3 embodiment of table 1~6 is provided
Cutting resistance (secondary) EN388 Pyatyi standards
Embodiment 1 30 It is cutting resistance >=20 times
Embodiment 2 28 It is cutting resistance >=20 times
Embodiment 3 27 It is cutting resistance >=20 times
Embodiment 4 25 It is cutting resistance >=20 times
Embodiment 5 21 It is cutting resistance >=20 times
Embodiment 6 21 It is cutting resistance >=20 times
As shown in Table 3, the present invention provide cut resistant superhigh molecular weight polyethylene fibers belt cutting-resisting property compared with Good, obtained glove can reach EN388 Pyatyi standards.
The described above of the disclosed embodiments, enables professional and technical personnel in the field to realize or using this Invention.Various modifications to these embodiments will be apparent for those skilled in the art , generic principles defined herein can without departing from the spirit or scope of the present invention, Realize in other embodiments.Therefore, the present invention is not intended to be limited to the embodiments shown herein, And it is to fit to the most wide scope consistent with principles disclosed herein and features of novelty.

Claims (10)

1. a kind of cut resistant superhigh molecular weight polyethylene fibers, it is characterised in that include:
Superhigh molecular weight polyethylene fibers;
The hard fibre being dispersed in the superhigh molecular weight polyethylene fibers and iron powder;
The mass ratio of the superhigh molecular weight polyethylene fibers, hard fibre and iron powder is 100:(3~6): (0.01~0.05).
2. cut resistant superhigh molecular weight polyethylene fibers according to claim 1, it is characterised in that The weight average molecular weight of the superhigh molecular weight polyethylene fibers is 3.0 × 106~5 × 106, molecular weight distribution≤ 9.0。
3. cut resistant superhigh molecular weight polyethylene fibers according to claim 1, it is characterised in that The hard fibre includes one or more in ceramic fibre, carbon fiber and silicon carbide whisker.
4. cut resistant superhigh molecular weight polyethylene fibers according to claim 1, it is characterised in that The average diameter of the hard fibre is less than or equal to 9 μm more than 0, and draw ratio is less than or equal to 30 more than 0.
5. cut resistant superhigh molecular weight polyethylene fibers according to claim 1, it is characterised in that The mean diameter of the iron powder is 10 μm~44 μm.
6. the preparation of the cut resistant superhigh molecular weight polyethylene fibers described in a kind of any one of Claims 1 to 5 Method, it is characterised in that comprise the following steps:
A) hard fibre, iron powder and solvent naphtha are mixed, obtains mixed liquor A;
B) mixed liquor A is mixed with ultra-high molecular weight polyethylene lysate, obtains spinning solution;
C) spinning solution is carried out successively spinning, preliminary draft, extraction, drying and positive drawing-off, obtain Cut resistant superhigh molecular weight polyethylene fibers.
7. preparation method according to claim 6, it is characterised in that solvent described in step a) Oil by 70%~95% the cycloalkane containing 25~50 carbon atoms and 5%~30% containing 25~50 carbon atoms Chain hydrocarbon composition.
8. preparation method according to claim 6, it is characterised in that hard described in step a) The mass ratio of fiber, iron powder and solvent naphtha is (3~6):(0.01~0.05):(10~24).
9. preparation method according to claim 6, it is characterised in that superelevation described in step b) Molecular weight polyethylene lysate includes:
100 weight portion of ultra-high molecular weight polyethylene;
800 weight portion~2800 weight portion of solvent naphtha.
10. the cut resistant superhigh molecular weight polyethylene fibers conduct described in a kind of any one of Claims 1 to 5 The application of cut resistant material.
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CN109610029A (en) * 2017-09-30 2019-04-12 中国石化仪征化纤有限责任公司 Fiber, fabric and preparation method thereof
CN113638106A (en) * 2021-09-03 2021-11-12 青岛信泰科技有限公司 Crease-resistant polyethylene fiber cloth and preparation method thereof

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