CN106555243B - A kind of cut resistant ultra high molecular weight polyethylene fiber and its preparation method and application - Google Patents
A kind of cut resistant ultra high molecular weight polyethylene fiber and its preparation method and application Download PDFInfo
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- CN106555243B CN106555243B CN201510616983.6A CN201510616983A CN106555243B CN 106555243 B CN106555243 B CN 106555243B CN 201510616983 A CN201510616983 A CN 201510616983A CN 106555243 B CN106555243 B CN 106555243B
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Abstract
The present invention provides a kind of cut resistant ultra high molecular weight polyethylene fiber and its preparation method and application, the cut resistant ultra high molecular weight polyethylene fiber includes: ultra high molecular weight polyethylene fiber；The hard fibre and hard fibre slag being dispersed in the ultra high molecular weight polyethylene fiber；The mass ratio of the ultra high molecular weight polyethylene fiber, hard fibre and hard fibre slag is 100:(3~6): (0.001~0.18).Compared with prior art, cut resistant ultra high molecular weight polyethylene fiber provided by the invention is on the basis of meeting belt cutting-resisting property five grade standard of EN388, hard fibre is set to be more evenly distributed in ultra-high molecular weight polyethylene by the way that hard fibre slag is added, to make finished fiber intensity homogeneity with higher, while improving the rub resistance of finished fiber.
Description
Technical field
The present invention relates to ultra high molecular weight polyethylene fiber technical fields, are that be related to a kind of cut resistant super more specifically
High molecular weight polyethylene fiber and its preparation method and application.
Background technique
Ultra high molecular weight polyethylene fiber, also known as high-strength high-modulus polyethylene fiber, refer to by relative molecular weight 1,000,000 with
On polyethylene spin come fiber.Since ultra high molecular weight polyethylene fiber has light weight, impact resistance, dielectric properties high
The advantages that, it is widely used in aerospace field, sea area defence field, weaponry field and daily industrial circle.
In daily industrial circle, ultra high molecular weight polyethylene fiber is most commonly employed to the production that preparation has cut resistant function
Product, for example, cut resistant gloves, cut resistant tent, cut resistant rope etc..But the supra polymer only prepared by polyethylene powders
The belt cutting-resisting property of weight polyethylene fiber is limited, and it is anti-that the belt cutting-resisting property for the industrial gloves being made from it is only capable of reaching industrial gloves
Protect the three-level requirement of European standard EN388 standard；And by adding glass fibre thereto, belt cutting-resisting property can be made to reach
The Pyatyi requirement of EN388 standard, but flexibility due to glass fibre and comfort are poor, and practical application is unsatisfactory.Therefore,
In practical application more be directed toward develop it is a kind of can reach EN388 Pyatyi requirement, simultaneously again soft comfortable supra polymer
Weight polyethylene fiber is used to prepare the products such as industrial gloves.
Currently, people improve finished product by the way that ingredient, the spinning technique of improvement ultra high molecular weight polyethylene fiber etc. are many-sided
The belt cutting-resisting property of fiber.Patent document US5976998 discloses a kind of filled cut-resistant fiber, the fiber by fibre-forming polymer and
Hard filler of the Moh's scale number greater than 3 is made.But the granularity of the hard filler due to using is small, dosage is few, hard is filled out
Material is difficult to reticulate distribution, therefore the ultra high molecular weight polyethylene fiber that this method obtains in ultra high molecular weight polyethylene fiber
Cutting resistance be not improved.
Patent document WO2008046476 discloses a kind of cut resistant yarn, described it includes silk thread and/or staple fibre
Silk thread and/or staple fibre include hard component for improving the cutting resistance of yarn, wherein the hard component is flat
Equal diameter is up to 25 μm of more hard fibres.Although the cutting resistance for the ultra high molecular weight polyethylene fiber that this method obtains
It is effectively improved, still, since hard component has lesser partial size and biggish specific surface area, hard component is inherently
Easily reunite, keep the intensity homogeneity of finished fiber poor, and since hard component is the biggish threadiness of draw ratio, flat
Row is not high in the rub resistance in machine direction, and aggregate performance is that quality stability is poor.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of cut resistant ultra high molecular weight polyethylene fiber and its preparation sides
The intensity homogeneity of method and application, cut resistant ultra high molecular weight polyethylene fiber provided by the invention is good and rub resistance is high.
The present invention provides a kind of cut resistant ultra high molecular weight polyethylene fibers, comprising:
Ultra high molecular weight polyethylene fiber；
The hard fibre and hard fibre slag being dispersed in the ultra high molecular weight polyethylene fiber；
The mass ratio of the ultra high molecular weight polyethylene fiber, hard fibre and hard fibre slag is 100:(3~6):
(0.001~0.18).
Preferably, the weight average molecular weight of the ultra high molecular weight polyethylene fiber is 3.0 × 106~5 × 106, molecular weight point
Cloth≤9.0.
Preferably, the hard fibre includes one of ceramic fibre, carbon fiber and silicon carbide whisker or a variety of.
Preferably, the average diameter of the hard fibre is greater than 0 and is less than or equal to 9 μm, and draw ratio is greater than 0 and is less than or equal to 30.
Preferably, the average grain diameter of the hard fibre slag is 30 μm~50 μm.
The present invention also provides a kind of preparations of cut resistant ultra high molecular weight polyethylene fiber described in above-mentioned technical proposal
Method, comprising the following steps:
A) hard fibre, hard fibre slag 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 successively spinned, preliminary draft, extraction, drying and positive drawing-off, obtains cut resistant superelevation
Molecular weight polyethylene fiber.
Preferably, solvent naphtha described in step a) by 70%~95% the cycloalkane and 5% containing 25~50 carbon atoms
~30% chain hydrocarbon composition containing 25~50 carbon atoms.
Preferably, the mass ratio of hard fibre described in step a), hard fibre slag and solvent naphtha is (3~6):
(0.001~0.18): (10~24).
Preferably, ultra-high molecular weight polyethylene lysate described in step b) includes:
100 parts by weight of ultra-high molecular weight polyethylene；
800 parts by weight of solvent naphtha~2800 parts by weight.
The present invention also provides cut resistant ultra high molecular weight polyethylene fibers described in a kind of above-mentioned technical proposal as resistance to
The application of cutting material.
It is described resistance to cut the present invention provides a kind of cut resistant ultra high molecular weight polyethylene fiber and its preparation method and application
Cutting ultra high molecular weight polyethylene fiber includes: ultra high molecular weight polyethylene fiber；It is fine to be dispersed in the ultra-high molecular weight polyethylene
Hard fibre and hard fibre slag in dimension；The ultra high molecular weight polyethylene fiber, hard fibre and hard fibre slag
Mass ratio be 100:(3~6): (0.001~0.18).Compared with prior art, cut resistant supra polymer provided by the invention
Weight polyethylene fiber makes hard on the basis of meeting belt cutting-resisting property five grade standard of EN388, by the way that hard fibre slag is added
Fiber is more evenly distributed in ultra-high molecular weight polyethylene, to make finished fiber intensity homogeneity with higher, mentions simultaneously
The rub resistance of high finished fiber.The experimental results showed that cut resistant ultra high molecular weight polyethylene fiber provided by the invention is strong
It spends change rate and is lower than 5%, rub resistance can reach 120,000 times or more.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of cut resistant ultra high molecular weight polyethylene fibers, comprising:
Ultra high molecular weight polyethylene fiber；
The hard fibre and hard fibre slag being dispersed in the ultra high molecular weight polyethylene fiber；
The mass ratio of the ultra high molecular weight polyethylene fiber, hard fibre and hard fibre slag is 100:(3~6):
(0.001~0.18).
In the present invention, the weight average molecular weight of the ultra high molecular weight polyethylene fiber 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 fiber is preferably≤9.0, more excellent
It is selected as 5.0.In the present invention, the ultra high molecular weight polyethylene fiber is the cut resistant ultra high molecular weight polyethylene fiber
Matrix, structural regularity with higher and consistency, so that making product integrally has the mechanical property of high-strength and high-modulus amount.
In the present invention, the hard fibre preferably include one of ceramic fibre, carbon fiber and silicon carbide whisker or
It is a variety of, the more preferably mixture of ceramic fibre, carbon fiber and silicon carbide whisker.In the present invention, the hard fibre is institute
The reinforcing material of cut resistant ultra high molecular weight polyethylene fiber is stated, the intensity of finished fiber can be effectively improved, it is resistance to improve product
Cutting performance；The present invention is not particularly limited the source of the hard fibre, using well known to those skilled in the art above-mentioned
The commercial goods of ceramic fibre, carbon fiber and silicon carbide whisker.In the present invention, the ceramic fibre, carbon fiber and carbon
The mass ratio of ceramic fibre, carbon fiber and silicon carbide whisker is preferably 1:(7~8.8 in the mixture of SiClx whisker): (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, and more preferably greater than 0 is less than or equal to 7 μm；The hard is fine
The draw ratio of dimension is preferably greater than 0 and is less than or equal to 30, more preferably greater than 0 less than or equal to 20.
In the present invention, the hard fibre slag be hard fibre by-product produced during the preparation process, composition with
Hard fibre is identical；The fiber forming process of the hard fibre rises in a flash brittleness viscosity model from the fibre forming viscosity range of melt
It encloses, obtains the hard fibre of threadiness, meanwhile, small part melt does not become threadiness and becomes granular, blocky or rodlike, obtains
Non-fibrous material, i.e. hard fibre slag；It, can using sedimentation since hard fibre is different from the density of hard fibre slag
Hard fibre and hard fibre slag are separated.In the present invention, the separation of the hard fibre and hard fibre slag
Method is preferred specifically:
Hard fibre is dispersed in petroleum ether, stands 5min after stirring 0.5h, then taken hard fibre with 270 mesh slurry net
Out, in triplicate, hard fibre and hard fibre slag are respectively obtained.In the present invention, the hard fibre slag can make
The hard fibre is more evenly distributed in ultra-high molecular weight polyethylene, while slowing down hard fibre and ultra-high molecular weight polyethylene
The effect of stress concentration existing for interface prevents micro-crack extension.In the present invention, the average grain diameter of the hard fibre slag is excellent
It is selected as 30 μm~50 μm, more preferably 35 μm~45 μm.
In the present invention, the mass ratio of the ultra high molecular weight polyethylene fiber, hard fibre and slag be 100:(3~
6): (0.001~0.18), preferably 100:(4~5): (0.018~0.09), more preferably 100:4.5:0.027.
The present invention also provides a kind of preparations of cut resistant ultra high molecular weight polyethylene fiber described in above-mentioned technical proposal
Method, comprising the following steps:
A) hard fibre, hard fibre slag 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 successively spinned, preliminary draft, extraction, drying and positive drawing-off, obtains cut resistant superelevation
Molecular weight polyethylene fiber.
In the present invention, hard fibre, hard fibre slag and solvent naphtha are mixed, obtains mixed liquor A.In the present invention
In, the hard fibre preferably includes one of ceramic fibre, carbon fiber and silicon carbide whisker or a variety of, more preferably ceramic
The mixture of fiber, carbon fiber and silicon carbide whisker.In the present invention, the hard fibre is the cut resistant super high molecular weight
The reinforcing material of polyethylene fibre can be effectively improved the intensity of finished fiber, improve product belt cutting-resisting property；The present invention is to institute
The source for stating hard fibre is not particularly limited, using above-mentioned ceramic fibre, carbon fiber and carbon well known to those skilled in the art
The commercial goods of SiClx whisker.In the present invention, it makes pottery in the mixture of the ceramic fibre, carbon fiber and silicon carbide whisker
The mass ratio of porcelain fiber, 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 hard fibre is averaged
Diameter is preferably greater than 0 less than or equal to 9 μm, and more preferably higher than 0 is less than or equal to 7 μm；The draw ratio of the hard fibre is preferred
It is less than or equal to 20 to be less than or equal to 30, more preferably higher than 0 greater than 0.
In the present invention, the hard fibre slag be hard fibre by-product produced during the preparation process, composition with
Hard fibre is identical；The fiber forming process of the hard fibre rises in a flash brittleness viscosity model from the fibre forming viscosity range of melt
It encloses, obtains the hard fibre of threadiness, meanwhile, small part melt does not become threadiness and becomes granular, blocky or rodlike, obtains
Non-fibrous material, i.e. hard fibre slag；It, can using sedimentation since hard fibre is different from the density of hard fibre slag
Hard fibre and hard fibre slag are separated.In the present invention, the separation of the hard fibre and hard fibre slag
Method is preferred specifically:
Hard fibre is dispersed in petroleum ether, stands 5min after stirring 0.5h, then taken hard fibre with 80 mesh slurry net
Out, in triplicate, hard fibre and hard fibre slag are respectively obtained.In the present invention, the hard fibre slag can make
The hard fibre is more evenly distributed in ultra-high molecular weight polyethylene, while slowing down hard fibre and ultra-high molecular weight polyethylene
The effect of stress concentration existing for interface prevents micro-crack extension.In the present invention, the average grain diameter of the hard fibre slag is excellent
It is selected as 30 μm~50 μm, more preferably 35 μm~45 μm.
In the present invention, the solvent naphtha preferably by 70%~95% the cycloalkane and 5% containing 25~50 carbon atoms
~30% chain hydrocarbon composition containing 25~50 carbon atoms, more preferably by 85%~90% the ring containing 25~50 carbon atoms
Alkane and 10%~15% the chain hydrocarbon composition containing 25~50 carbon atoms, most preferably white oil.In the present invention, the solvent
The kinematic viscosity of oil is preferably 61.2mm2/ s~74.8mm2/s；The present invention is not particularly limited the source of the solvent naphtha, adopts
With 5# white oil well known to those skilled in the art, 7# white oil, 10# white oil, 15# white oil, 22# white oil, 26# white oil, 32# white oil,
The commercial goods of 46# white oil, 68# white oil, 70# white oil, 100# white oil and 150# white oil.In the present invention, the solvent
Oil is the solvent of ultra-high molecular weight polyethylene lysate, and hard fibre and hard fibre slag are dispersed in by the present invention first
In solvent naphtha, be conducive to the further dispersion of hard fibre and hard fibre slag in ultra high molecular weight polyethylene fiber.
In the present invention, after hard fibre, hard fibre slag and solvent naphtha being mixed, the fortune of obtained mixed solution A
Kinetic viscosity can change according to the additional amount of hard fibre and hard fibre slag, have an impact to the mechanical property of product, add
Enter that amount is excessively high, the kinematic viscosity of mixed solution A reduces, and product broken end number can be made to increase, additional amount is too low, is unfavorable for fibre strength
Raising, make the cutting resistance and strength reduction of product.In the present invention, by hard fibre, hard fibre slag and solvent naphtha
Mixing；The mass ratio of the hard fibre, hard fibre slag and solvent naphtha is preferably (3~6): (0.001~0.18): (10
~24), more preferably (4~5): (0.018~0.09): (14~20).
In the present invention, the mixed process is preferred specifically:
Hard fibre, slag and solvent naphtha are mixed under stirring conditions.Method of the present invention to the stirring
It is not particularly limited, using artificial stirring well known to those skilled in the art or mechanical stirring.In the present invention, described to stir
The speed mixed is preferably 1000rpm~4500rpm, more preferably 2000rpm~3000rpm；The present invention does not have the time of stirring
Have specifically limited, hard fibre and slag is made to be uniformly dispersed in solvent naphtha.
After obtaining the mixed liquor A, the present invention mixes the mixed liquor A with ultra-high molecular weight polyethylene lysate, obtains
To spinning solution.In the present invention, the ultra-high molecular weight polyethylene lysate preferably includes:
100 parts by weight of ultra-high molecular weight polyethylene；
800 parts by weight of solvent naphtha~2800 parts by weight.
In the present invention, the ultra-high molecular weight polyethylene is molten in the solvent naphtha by ultra-high molecular weight polyethylene powder
It is obtained after solution；The present invention is not particularly limited the source of the ultra-high molecular weight polyethylene powder, using those skilled in the art
Commercial goods known to member.In the present invention, the weight average molecular weight of the ultra-high molecular weight polyethylene 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
It is preferred that≤9.0, more preferably 5.0；The partial size of the ultra-high molecular weight polyethylene powder is preferably 40 mesh~100 mesh, more preferably
For 60 mesh~80 mesh.In the present invention, the ultra-high molecular weight polyethylene lysate preferably includes ultra-high molecular weight polyethylene 100
Parts by weight.
In the present invention, the solvent naphtha preferably by 70%~95% the cycloalkane and 5% containing 25~50 carbon atoms
~30% chain hydrocarbon composition containing 25~50 carbon atoms, more preferably by 85%~90% the ring containing 25~50 carbon atoms
Alkane and 10%~15% the chain hydrocarbon composition containing 25~50 carbon atoms, most preferably white oil.In the present invention, the solvent
The initial boiling point of oil is higher than 450 DEG C；The kinematic viscosity of the solvent naphtha is preferably 61.2mm2/ s~74.8mm2/s；The present invention is to institute
The source for stating solvent naphtha is not particularly limited, using 5# white oil well known to those skilled in the art, 7# white oil, 10# white oil, 15#
White oil, 22# white oil, 26# white oil, 32# white oil, 46# white oil, 68# white oil, 70# white oil, 100# white oil and 150# white oil it is commercially available
Commodity.In the present invention, the solvent naphtha in the ultra-high molecular weight polyethylene lysate with it is molten in the mixed solution A
Agent oil is preferably identical solvent naphtha, is conducive to the miscible of the ultra-high molecular weight polyethylene lysate and the mixed solution A.
In the present invention, the ultra-high molecular weight polyethylene lysate preferably includes 800 parts by weight of solvent naphtha~2800 parts by weight, more excellent
It is selected as 1100 parts by weight~2000 parts by weight.
In the present invention, the preparation method of the ultra-high molecular weight polyethylene lysate is preferred specifically:
Ultra-high molecular weight polyethylene powder is mixed with solvent naphtha, obtains ultra-high molecular weight polyethylene lysate.In this hair
In bright, the process that ultra-high molecular weight polyethylene powder is mixed with solvent naphtha is preferred specifically:
Ultra-high molecular weight polyethylene powder is added in solvent naphtha, is stirred, it is molten to obtain ultra-high molecular weight polyethylene
Solve liquid.The present invention is not particularly limited the method for the stirring, using artificial stirring well known to those skilled in the art or machine
Tool stirring.In the present invention, the speed of the stirring is preferably 30rpm~500rpm, and 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 excellent
It is selected as 0.5h~5h, more preferably 1h~2h.
In the present invention, the mixed liquor A is mixed with ultra-high molecular weight polyethylene lysate, obtains spinning solution.?
In the present invention, the process that mixed liquor A is mixed with ultra-high molecular weight polyethylene lysate is preferred specifically:
Mixed liquor A is added in ultra-high molecular weight polyethylene lysate, is stirred, spinning solution is obtained.The present invention
The method of the stirring is not particularly limited, using artificial stirring well known to those skilled in the art or mechanical stirring.
In the present invention, the speed of the stirring is preferably 60rpm~100rpm, more preferably 80rpm~90rpm；The stirring
Temperature is preferably 100 DEG C~160 DEG C, more preferably 120 DEG C~140 DEG C；The time of the stirring is preferably 1h~6h, more preferably
For 2h~3h.
After obtaining spinning solution, the present invention successively spins the spinning solution, preliminary draft, extraction, drying and just
Drawing-off obtains cut resistant ultra high molecular weight polyethylene fiber.In the present invention, spinning solution is spinned, obtains gel fiber.
In the present invention, the process of the spinning is preferred specifically:
The spinning solution is successively filtered, spinneret and cooling, obtains gel fiber.In the present invention, by the spinning
Silk stock solution is filtered.The present invention is not particularly limited the equipment of the filtering, it is preferred to use filter；The filter
Aperture is preferably 30 mesh~100 mesh, more preferably 60 mesh~70 mesh.
After completing the filter process, filtered spinning solution is carried out spinneret and cooling by the present invention, obtains gel fiber.
In the present invention, the equipment of the spinneret is preferably manifold, and it is not specifically limited to this by the present invention；The present invention will be through manifold
The product obtained after spinneret, is directly cooled down, and gel fiber is obtained.The present invention is not particularly limited the method for the cooling,
It is preferred that using the technical solution of water-bath cooling well known to those skilled in the art；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.In the present invention, institute
Stating preliminary draft can reduce the internal stress of gel fiber internal residual.In the present invention, the draft ratio of the preliminary draft is preferably 1
~10 times, more preferably 3~5 times；The temperature of the preliminary draft is preferably 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
In, the purpose of the extraction is the solvent naphtha removed in gel fiber.In the present invention, extractant used in the extraction process is excellent
It is selected as one of white oil extractant, n-hexane, gasoline and tetrahydro carbon or a variety of.In the present invention, the extractant is to molten
Agent oil has good intermiscibility, and the present invention is not particularly limited the source of the extractant, using those skilled in the art
The commercial goods of well known above-mentioned white oil extractant, n-hexane, gasoline and tetrahydro carbon.In the present invention, the drying
Purpose be that extractant is made to volatilize.In the present invention, the temperature of the drying is preferably 25 DEG C~45 DEG C, more preferably 30 DEG C~
40℃。
After completing the extraction and drying process, the gel fiber after extraction and drying is carried out positive drawing-off by the present invention, is obtained
Cut resistant ultra high molecular weight polyethylene fiber.In the present invention, the temperature of the positive drawing-off is preferably 120 DEG C~160 DEG C, more excellent
It is selected as 140 DEG C~150 DEG C；The draft ratio of the positive drawing-off is preferably 4~20 times, and more preferably 6~10 times.In the present invention
In, the positive drawing-off can make fiber deform, and obtain finished fiber, mechanical property of the fibre deformation speed to product
It has a major impact, the deformation velocity such as fruit fiber is too fast, then fiber is broken before reaching enough draft ratios, and fiber
Deformation velocity it is excessively slow, then crystallize during stretching relatively slow, crystal zone formation is not fine and close continuous, 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。
The present invention also provides cut resistant ultra high molecular weight polyethylene fibers described in a kind of above-mentioned technical proposal as resistance to
The application of cutting material.In the present invention, the cut resistant material is the product with cut resistant function, preferably cut-resistant yarn
Line.The present invention is not particularly limited the preparation method of the cut resistant yarn, using yarn well known to those skilled in the art
The method of processing.In the present invention, the cut resistant yarn can be by being knitted or weaving to obtain different types of resistance to cut
Cut product, such as cut resistant gloves, cut resistant tent, cut resistant rope.
It is described resistance to cut the present invention provides a kind of cut resistant ultra high molecular weight polyethylene fiber and its preparation method and application
Cutting ultra high molecular weight polyethylene fiber includes: ultra high molecular weight polyethylene fiber；It is fine to be dispersed in the ultra-high molecular weight polyethylene
Hard fibre and hard fibre slag in dimension；The ultra high molecular weight polyethylene fiber, hard fibre and hard fibre slag
Mass ratio be 100:(3~6): (0.001~0.18).Compared with prior art, cut resistant supra polymer provided by the invention
Weight polyethylene fiber makes hard on the basis of meeting belt cutting-resisting property five grade standard of EN388, by the way that hard fibre slag is added
Fiber is more evenly distributed in ultra-high molecular weight polyethylene, to make finished fiber intensity homogeneity with higher, mentions simultaneously
The rub resistance of high finished fiber.The experimental results showed that cut resistant ultra high molecular weight polyethylene fiber provided by the invention is strong
It spends change rate and is lower than 5%, rub resistance can reach 120,000 times or more.
In addition, the elongation at break of cut resistant ultra high molecular weight polyethylene fiber provided by the invention it is higher and broken end number compared with
Low, quality stability is high, and industrial gloves belt cutting-resisting property obtained is excellent.
In order to further illustrate the present invention, it is described in detail below by following embodiment.Following embodiment of the present invention
Ultra-high molecular weight polyethylene powder used is provided by Yanshan Petrochemical；Ceramic fibre used is mentioned by Shandong Luyang share co.,ltd
For the average diameter of the ceramic fibre is less than or equal to 9 μm, and draw ratio is less than or equal to 30；Carbon fiber used multiple Condor carbon in
Fiber Co., Ltd provides, and the average diameter of the carbon fiber is less than or equal to 9 μm, and draw ratio is less than or equal to 30；Silicon carbide used
Whisker is provided by one promise new high-tech material development corporation, Ltd. of Qinhuangdao, and the average diameter of the silicon carbide whisker is less than or equal to 9 μm,
Draw ratio is less than or equal to 30；The average grain diameter of hard fibre slag used is 35 μm~45 μm；White oil used is by Total SA
It provides；White oil extractant used is provided by Shanghai Xi Le Chemical Co., Ltd..
Embodiment 1
(1) 1.8kg is added in 50g ceramic fibre, 375g carbon fiber, 25g silicon carbide whisker and 2.7g hard fibre slag
In 68# white oil, it is stirred until homogeneous at 2500rpm, obtains mixed liquor A.
It (2) is 4.2 × 10 by 10kg weight average molecular weight6, molecular weight distribution be 5.0 ultra-high molecular weight polyethylene powder add
Enter in 160kg 68# white oil, stirs 1.5h at 80rpm, 105 DEG C, obtain ultra-high molecular weight polyethylene lysate；Again described
The mixed liquor A that step (1) obtains is added in ultra-high molecular weight polyethylene lysate, stirs 2.5h at 85rpm, 130 DEG C, obtains
Spinning solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then after manifold spinneret, product is lauched at 25 DEG C
Bath cooling, obtains gel fiber；Then the gel fiber is subjected to preliminary draft with 4 times of draft ratio at 25 DEG C, then through white oil
It is dry at 40 DEG C after extractant extraction, positive drawing-off is finally carried out with 7 times of draft ratio at 145 DEG C, controls the change of fiber
Shape speed is 0.020s-1, obtain cut resistant ultra high molecular weight polyethylene fiber.
Embodiment 2
(1) 1.4kg is added in 50g ceramic fibre, 385g carbon fiber, 15g silicon carbide whisker and 1.8g hard fibre slag
In 68# white oil, it is stirred until homogeneous at 2000rpm, obtains mixed liquor A.
It (2) is 3.5 × 10 by 10kg weight average molecular weight6, molecular weight distribution be 5.0 ultra-high molecular weight polyethylene powder add
Enter in 110kg 68# white oil, stirs 2h at 60rpm, 100 DEG C, obtain ultra-high molecular weight polyethylene lysate；Again described super
The mixed liquor A that step (1) obtains is added in High molecular weight polyethylene lysate, stirs 3h at 80rpm, 120 DEG C, obtains spinning
Stoste.
(3) filter that spinning solution via hole diameter is 70 mesh is filtered, then after manifold spinneret, product is lauched at 22 DEG C
Bath cooling, obtains gel fiber；Then the gel fiber is subjected to preliminary draft with 5 times of draft ratio at 25 DEG C, then through white oil
It is dry at 40 DEG C after extractant extraction, positive drawing-off is finally carried out with 6 times of draft ratio at 140 DEG C, controls the change of fiber
Shape speed is 0.025s-1, obtain cut resistant ultra high molecular weight polyethylene fiber.
Embodiment 3
(1) 2.0kg is added in 56g ceramic fibre, 417g carbon fiber, 28g silicon carbide whisker and 9g hard fibre slag
It in 68# white oil, is stirred until homogeneous at 3,000 rpm, obtains mixed liquor A.
It (2) is 4.5 × 10 by 10kg weight average molecular weight6, molecular weight distribution be 5.0 ultra-high molecular weight polyethylene powder add
Enter in 200kg 68# white oil, stirs 1h at 100rpm, 110 DEG C, obtain ultra-high molecular weight polyethylene lysate；Again described
The mixed liquor A that step (1) obtains is added in ultra-high molecular weight polyethylene lysate, stirs 2h at 90rpm, 140 DEG C, is spun
Silk stock solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then after manifold spinneret, product is lauched at 25 DEG C
Bath cooling, obtains gel fiber；Then the gel fiber is subjected to preliminary draft with 3 times of draft ratio at 25 DEG C, then through white oil
It is dry at 40 DEG C after extractant extraction, positive drawing-off is finally carried out with 8 times of draft ratio at 150 DEG C, controls the change of fiber
Shape speed is 0.0118s-1, obtain cut resistant ultra high molecular weight polyethylene fiber.
Embodiment 4
(1) 450g ceramic fibre and 2.7g hard fibre slag are added in 1.8kg 68# white oil, are stirred at 2500rpm
It mixes to uniform, obtains mixed liquor A.
It (2) is 4.2 × 10 by 10kg weight average molecular weight6, molecular weight distribution be 5.0 ultra-high molecular weight polyethylene powder add
Enter in 160kg 68# white oil, stirs 1.5h at 80rpm, 105 DEG C, obtain ultra-high molecular weight polyethylene lysate；Again described
The mixed liquor A that step (1) obtains is added in ultra-high molecular weight polyethylene lysate, stirs 2.5h at 85rpm, 130 DEG C, obtains
Spinning solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then after manifold spinneret, product is lauched at 25 DEG C
Bath cooling, obtains gel fiber；Then the gel fiber is subjected to preliminary draft with 4 times of draft ratio at 25 DEG C, then through white oil
It is dry at 30 DEG C after extractant extraction, positive drawing-off is finally carried out with 7 times of draft ratio at 145 DEG C, controls the change of fiber
Shape speed is 0.020s-1, obtain cut resistant ultra high molecular weight polyethylene fiber.
Embodiment 5
(1) 450g carbon fiber and 2.7g hard fibre slag are added in 1.8kg 68# white oil, are stirred at 2500rpm
To uniform, mixed liquor A is obtained.
It (2) is 4.2 × 10 by 10kg weight average molecular weight6, molecular weight distribution be 5.0 ultra-high molecular weight polyethylene powder add
Enter in 160kg 68# white oil, stirs 1.5h at 80rpm, 105 DEG C, obtain ultra-high molecular weight polyethylene lysate；Again described
The mixed liquor A that step (1) obtains is added in ultra-high molecular weight polyethylene lysate, stirs 2.5h at 85rpm, 130 DEG C, obtains
Spinning solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then after manifold spinneret, product is lauched at 25 DEG C
Bath cooling, obtains gel fiber；Then the gel fiber is subjected to preliminary draft with 4 times of draft ratio at 25 DEG C, then through white oil
It is dry at 30 DEG C after extractant extraction, positive drawing-off is finally carried out with 7 times of draft ratio at 145 DEG C, controls the change of fiber
Shape speed is 0.020s-1, obtain cut resistant ultra high molecular weight polyethylene fiber.
Embodiment 6
(1) 450g silicon carbide whisker and 2.7g hard fibre slag are added in 1.8kg 68# white oil, at 2500rpm
It is stirred until homogeneous, obtains mixed liquor A.
It (2) is 4.2 × 10 by 10kg weight average molecular weight6, molecular weight distribution be 5.0 ultra-high molecular weight polyethylene powder add
Enter in 160kg 68# white oil, stirs 1.5h at 80rpm, 105 DEG C, obtain ultra-high molecular weight polyethylene lysate；Again described
The mixed liquor A that step (1) obtains is added in ultra-high molecular weight polyethylene lysate, stirs 2.5h at 85rpm, 130 DEG C, obtains
Spinning solution.
(3) filter that spinning solution via hole diameter is 60 mesh is filtered, then after manifold spinneret, product is lauched at 25 DEG C
Bath cooling, obtains gel fiber；Then the gel fiber is subjected to preliminary draft with 4 times of draft ratio at 25 DEG C, then through white oil
It is dry at 30 DEG C after extractant extraction, positive drawing-off is finally carried out with 7 times of draft ratio at 145 DEG C, controls the change of fiber
Shape speed is 0.020s-1, obtain cut resistant ultra high molecular weight polyethylene fiber.
Examples 1 to 6 is mentioned using DXLL-20000 electronic tensile machine method according to specified in GBT 19975-2005
Fibre strength, modulus and the elongation at break of the cut resistant ultra high molecular weight polyethylene fiber of confession are tested, using YG086 type
Measuring reel tests the fiber number for the cut resistant ultra high molecular weight polyethylene fiber that Examples 1 to 6 provides, and is connecing silk
Broken end number is obtained in the process, and the broken end number is expressed as the every myriametre broken end number of finished fiber.Test result is as shown in table 1.
The fibre strength data for the cut resistant ultra high molecular weight polyethylene fiber that 1 Examples 1 to 6 of table provides
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Intensity (cN/dtex) | 26.8 | 26.7 | 26.5 | 25.5 | 25.1 | 24.8 |
| Modulus (cN/dtex) | 987 | 980 | 977 | 880 | 860 | 833 |
| Fiber number (denier) | 401.5 | 396 | 440 | 419 | 412.5 | 429 |
| Elongation at break (%) | 4.5 | 4.3 | 4.0 | 3.8 | 3.8 | 3.2 |
| Break end number (a/myriametre) | 1.4 | 1.3 | 1.0 | 1.2 | 1.0 | 1.3 |
Using the intensity for the cut resistant ultra high molecular weight polyethylene fiber that Instron type puller system provides Examples 1 to 6
Change rate is tested, while poly- using the cut resistant super high molecular weight that YG086 type measuring reel provides Examples 1 to 6
Vinyl fiber distinguishes a large amount of fiber number data of follow-on test, then calculates fiber number coefficient of variation CV value, test result by variance
As shown in table 2.
The change rate of strength data for the cut resistant ultra high molecular weight polyethylene fiber that 2 Examples 1 to 6 of table provides
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Change rate of strength | 3.0% | 3.2% | 3.8% | 4.1% | 4.6% | 5.0% |
| Fiber number coefficient of variation CV | 0.5% | 0.8% | 0.8% | 1.0% | 1.3% | 1.5% |
It is higher that test result shows that the cut resistant ultra high molecular weight polyethylene fiber that the embodiment of the present invention 1~6 provides has
Fibre strength, while the change rate of strength of finished fiber is lower, i.e., strength stability is good；In addition, the product fiber number coefficient of variation
CV is lower, while product elongation at break is stablized, and broken end number is lower, to guarantee that product has preferable uniformity and quality steady
It is qualitative.
The cut resistant ultra high molecular weight polyethylene fiber that Example 1~6 provides, is twined along spool by positive and negative direction respectively
Around, the cut resistant yarn of 400D is made, then above-mentioned cut resistant yarn is coated, is woven, respectively obtain cut resistant industry
Gloves.European standard EN388 standard is protected according to industrial gloves, opponent, which covers, carries out anti-cut performance test, and number is worn out in measurement,
Two samples are taken every time, are measured five times, are averaged according to coefficient calculating；According to resistance in yarn test method (JISL1095)
Abrasion test method B, to Examples 1 to 6 provide 400D cut resistant yarn carry out rub resistance test, use diameter for
The converted steel of 0.9mm carries out CONTACT WITH FRICTION, indicates rub resistance by rubbing sample to be tested to the reciprocal time of fracture, surveys
Amount is averaged three times, and test condition is as follows: load 0.5g/D, and friction rate is 115 beats/min, and reciprocating motion length is
2.5cm, rubbing angle are 110 °.Test result is as shown in table 3.
The cut resistant ultra high molecular weight polyethylene fiber belt cutting-resisting property data that 3 Examples 1 to 6 of table provides
| Anti-cut (secondary) | Rub resistance (secondary) | Five grade standard of EN388 | |
| Embodiment 1 | 29 | 153553 | Anti-cut >=20 time |
| Embodiment 2 | 27 | 131110 | Anti-cut >=20 time |
| Embodiment 3 | 25 | 109048 | Anti-cut >=20 time |
| Embodiment 4 | 25 | 107400 | Anti-cut >=20 time |
| Embodiment 5 | 22 | 82692 | Anti-cut >=20 time |
| Embodiment 6 | 21 | 80210 | Anti-cut >=20 time |
As shown in Table 3, the belt cutting-resisting property of cut resistant ultra high molecular weight polyethylene fiber provided by the invention is preferable, is made
Gloves can reach five grade standard of EN388, while rub resistance is higher.
The above description of the disclosed embodiments, enables those skilled in the art to implement or use the present invention.It is right
A variety of modifications of these embodiments will be readily apparent to those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed herein
Widest scope.
Claims (9)
1. a kind of cut resistant ultra high molecular weight polyethylene fiber characterized by comprising
Ultra high molecular weight polyethylene fiber；
The hard fibre and hard fibre slag being dispersed in the ultra high molecular weight polyethylene fiber；
The mass ratio of the ultra high molecular weight polyethylene fiber, hard fibre and hard fibre slag is 100:(4~5):
(0.018~0.09)；
The preparation method of the cut resistant ultra high molecular weight polyethylene fiber, comprising the following steps:
A) hard fibre, hard fibre slag 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 successively spinned, preliminary draft, extraction, drying and positive drawing-off, obtains cut resistant supra polymer
Weight polyethylene fiber；
The temperature of the positive drawing-off is 140 DEG C~150 DEG C, and draft ratio is 6~10 times, and the deformation velocity for controlling fiber is
0.01s-1~0.1s-1。
2. cut resistant ultra high molecular weight polyethylene fiber according to claim 1, which is characterized in that the super high molecular weight
The weight average molecular weight of polyethylene fibre is 3.0 × 106~5 × 106, molecular weight distribution≤9.0.
3. cut resistant ultra high molecular weight polyethylene fiber according to claim 1, which is characterized in that the hard fibre packet
Include one of ceramic fibre, carbon fiber and silicon carbide whisker or a variety of.
4. cut resistant ultra high molecular weight polyethylene fiber according to claim 1, which is characterized in that the hard fibre
Average diameter is greater than 0 and is less than or equal to 9 μm, and draw ratio is greater than 0 and is less than or equal to 30.
5. cut resistant ultra high molecular weight polyethylene fiber according to claim 1, which is characterized in that the hard fibre mine
The average grain diameter of slag is 30 μm~50 μm.
6. cut resistant ultra high molecular weight polyethylene fiber according to claim 1, which is characterized in that molten described in step a)
Agent oil is by 70%~95% cycloalkane for containing 25~50 carbon atoms and 5%~30% chain hydrocarbon containing 25~50 carbon atoms
Composition.
7. cut resistant ultra high molecular weight polyethylene fiber according to claim 1, which is characterized in that hard described in step a)
The mass ratio of matter fiber, hard fibre slag and solvent naphtha is (3~6): (0.001~0.18): (10~24).
8. cut resistant ultra high molecular weight polyethylene fiber according to claim 1, which is characterized in that surpass described in step b)
High molecular weight polyethylene lysate includes:
100 parts by weight of ultra-high molecular weight polyethylene；
800 parts by weight of solvent naphtha~2800 parts by weight.
9. a kind of cut resistant ultra high molecular weight polyethylene fiber according to any one of claims 1 to 8 is as cut resistant material
Using.
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| CN115787121A (en) * | 2022-12-12 | 2023-03-14 | 浙江千禧龙纤特种纤维股份有限公司 | Cutting-resistant ultra-high molecular weight polyethylene fiber and preparation method and application thereof |
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| CN1182811A (en) * | 1996-11-19 | 1998-05-27 | 赫希斯特人造丝公司 | Cutting-resistant fibre for filling |
| CN101886295A (en) * | 2009-05-11 | 2010-11-17 | 胡盼盼 | Ultra-high molecular weight polyethylene colored fibers and preparation method thereof |
| CN102277669A (en) * | 2006-10-17 | 2011-12-14 | 帝斯曼知识产权资产管理有限公司 | Cut resistant yarn, a process for producing the yarn and products containing the yarn |
| CN104746165A (en) * | 2015-04-07 | 2015-07-01 | 中国科学技术大学 | Ultra-high molecular weight polyethylene porous fiber and preparation method thereof |
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| CN1182811A (en) * | 1996-11-19 | 1998-05-27 | 赫希斯特人造丝公司 | Cutting-resistant fibre for filling |
| CN102277669A (en) * | 2006-10-17 | 2011-12-14 | 帝斯曼知识产权资产管理有限公司 | Cut resistant yarn, a process for producing the yarn and products containing the yarn |
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