CN103276465B - Ultrahigh molecular weight polyethylene fiber and preparation method thereof - Google Patents
Ultrahigh molecular weight polyethylene fiber and preparation method thereof Download PDFInfo
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Abstract
The invention provides an ultrahigh molecular weight polyethylene fiber and a preparation method thereof. The method comprises the steps of making a ultrahigh molecular weight polyethylene fiber spinning solution into gelatinized pre-oriented yarns; performing balancing and standing treatment on the gelatinized pre-oriented yarns; performing pre-stretching, extracting, drying and positive stretching successively on the gelatinized pre-oriented yarns after the balancing and standing treatment; and coating an antistatic oil agent aqueous solution during the positive stretching, and thus the ultrahigh molecular weight polyethylene fiber is obtained, wherein the antistatic oil agent is a mixture of a polyoxyethylene ether antistatic agent and an anionic antistatic agent; viscosity of the antistatic oil agent at the temperature of 20 DEG C is 80 mPa.s-90 mPa.s; and a mass concentration of the antistatic oil agent aqueous solution is 0.5%-3%. The polyethylene fiber prepared by the method has relatively low static while keeping high strength and high modulus, thereby facilitating applications. A static voltage of the ultrahigh molecular weight polyethylene fiber provided by the invention is smaller than 0.2 kV.
Description
Technical field
The present invention relates to technical field of fiber preparation, particularly a kind of superhigh molecular weight polyethylene fibers and preparation method thereof.
Background technology
Superhigh molecular weight polyethylene fibers (be called for short UHMWPE), also claims high-strength high-modulus polyethylene fiber, refers to by the polyethylene of relative molecular weight more than 1,000,000 successively through a kind of high-performance fiber that spinning, extraction, drying and ultra-drawing are made.Quality is light, shock-resistant, dielectric properties advantages of higher to adopt the fibre reinforced composites made of superhigh molecular weight polyethylene fibers to have, and is widely used in aerospace field, defence field, marine site, weaponry field and daily industrial circle etc.
In the prior art, what prepare that superhigh molecular weight polyethylene fibers adopts usually is gel spinning technology.This technology uses the polyethylene of relative molecular weight more than 1,000,000 as raw material usually, first by this raw material and suitable solvent, to mix the swelling suspension obtained as spinning solution, then this spinning solution is twined through the shearing of screw extruder, even mixed, solution, carry out extruding stretching-condensation through spinning pack more shaping, thus obtain gelation pre-oriented yarn, finally this gelation pre-oriented yarn is carried out extracting, dry and ultra-drawing, obtain superhigh molecular weight polyethylene fibers.
In the production process of superhigh molecular weight polyethylene fibers, owing to being attended by the contour friction link of solvent extraction, drying, hot-stretch and high-speed winding, tow and finished fiber all very easily produce electrostatic.In the hot-stretch stage, if the electrostatic that tow produces is comparatively large, the coherent of tow is poor, and so, tow will occur when reeling mutually and twine phenomenon, causes broken end number to increase.If the electrostatic of finished fiber is comparatively large, a branch of synnema will fluffy, scatter, carry out very easily occurring to hang the situations such as silk guide frame when unwinding is produced in downstream application, cause end breakage rate to increase, affect production and processing.But, for the electrostatic problem how well solving superhigh molecular weight polyethylene fibers, yet there are no report.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of superhigh molecular weight polyethylene fibers and preparation method thereof, the method can make finished product polyethylene fiber while maintenance high strength, high-modulus, has lower electrostatic, is beneficial to application.
The invention provides a kind of preparation method of superhigh molecular weight polyethylene fibers, comprising:
A) ultra-high molecular weight polyethylene spinning solution is made gelation preorientation strand;
B) described gelation preorientation strand is carried out balance standing process;
C) described balance is left standstill the gelation preorientation strand after process and carry out preliminary draft, extraction, drying and positive drawing-off successively, and while positive drawing-off, apply the antistatic finish aqueous solution, obtain superhigh molecular weight polyethylene fibers;
Described antistatic finish is the mixture of Polyoxyethylene Ether antistatic additive and anionic antistatic agent, and described antistatic finish viscosity at 20 DEG C is 80mPas ~ 90mPas, and the mass concentration of the described antistatic finish aqueous solution is 0.5% ~ 3%.
Preferably, the water in the described antistatic finish aqueous solution is the soft water that hardness is less than 0.09 mM/l of alkaline earth ion concentration.
Preferably, the pH value of described antistatic finish is 6.8 ~ 7.2.
Preferably, the described antistatic finish aqueous solution adopts oiling roller to apply.
Preferably, the surface roughness Ra of described oiling roller is 0.3 ~ 1.5.
Preferably, upper speed oil during described coating is 15m/min ~ 25m/min, and the oil content on gained superhigh molecular weight polyethylene fibers is 1% ~ 5%.
Preferably, described positive drawing-off comprises the positive drawing-off of the first order, the positive drawing-off in the second level and the positive drawing-off of the third level, after the first drawing roller of the positive drawing-off in the described second level, apply the antistatic finish aqueous solution before the hot bellows of the positive drawing-off in the second level.
Preferably, the drawing-off general times applied described gelation pre-oriented yarn bar in described preliminary draft, extraction, drying and positive drafting process is 30 ~ 55.
Preferably, the temperature of the drying between described extraction and positive drawing-off is 40 DEG C ~ 80 DEG C.
The present invention also provides a kind of superhigh molecular weight polyethylene fibers, and its preparation method by mentioned earlier obtains, the electrostatic pressure < 0.2kV of described superhigh molecular weight polyethylene fibers.
Compared with prior art, first ultra-high molecular weight polyethylene spinning solution is made gelation preorientation strand by the present invention, then described gelation preorientation strand is carried out balancing and leave standstill process, finally described balance is left standstill the gelation preorientation strand after process and carry out preliminary draft, extraction, drying and positive drawing-off successively, and while positive drawing-off, apply the antistatic finish aqueous solution, obtain superhigh molecular weight polyethylene fibers; Described antistatic finish is the mixture of Polyoxyethylene Ether antistatic additive and anionic antistatic agent, and described antistatic finish viscosity at 20 DEG C is 80mPas ~ 90mPas, and the mass concentration of the described antistatic finish aqueous solution is 0.5% ~ 3%.The present invention adopts Polyoxyethylene Ether antistatic additive and the composite antistatic finish of anionic antistatic agent, and control its viscosity, because the viscosity of described antistatic finish is very low, fine with the miscible effect of water, in solution, oil concentration is very low, and on fiber, oil content (OPU) is also very low, so while performance antistatic property, very little on the fiber number impact of fiber, substantially do not affect the mechanical property of fiber.Further, the permeability of described antistatic finish is very good, and can enter in fibre structure fast, have good attachment fastness, when downstream application, antistatic property exists for a long time.In addition, the present invention applies the described antistatic finish aqueous solution while positive drawing-off, makes antistatic finish directly be coated on fiber surface, avoids the loss of antistatic finish addition, thus makes the antistatic effect of fiber better.
Further, the present invention adopts oiling roller to apply the described antistatic finish aqueous solution, when there is fracture of wire in the positive drafting production line of speed, can not doubling curling round the roll, to guarantee production efficiency and product quality all more favourable.
Further, for viscosity, very low and pH value is close to this antistatic finish of water, and the present invention adopts the comparatively coarse oiling roller of surface smoothness to apply its aqueous solution, can make to oil more even.
Further, described positive drawing-off comprises the positive drawing-off of the first order, the positive drawing-off in the second level and the positive drawing-off of the third level, the present invention is after the first drawing roller of the positive drawing-off in the described second level and apply the antistatic finish aqueous solution before the hot bellows of the positive drawing-off in the second level, by the heating of two baking ovens of the positive drawing-off in the second level below and the positive drawing-off of the third level, the moisture on tow can be dried, drying is carried out without the need to heating blower again, energy-saving and cost-reducing.Secondly; described antistatic finish temperature tolerance is better; after drawing-off by the larger multiple of the positive drawing-off of the first order; one can be avoided to lead the generation of large multiplying power chap, in addition, the extending uniform fold of finish is in tow surface; in two baking ovens of the positive drawing-off in the second level below and the positive drawing-off of the third level during drawing-off; easily fracture of wire place is occurring, the finish being coated on tow surface can play corresponding protective effect to tow, avoids the generation of lousiness.Moreover in positive drawing-off place of the first order, tow is less likely to occur heat most and leads fracture, make antistatic finish be coated on tow surface herein, the impact caused by lousiness is less, thus can ensure the stability of production.
Detailed description of the invention
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention provides a kind of preparation method of superhigh molecular weight polyethylene fibers, comprising:
A) ultra-high molecular weight polyethylene spinning solution is made gelation preorientation strand;
B) described gelation preorientation strand is carried out balance standing process;
C) described balance is left standstill the gelation preorientation strand after process and carry out preliminary draft, extraction, drying and positive drawing-off successively, and while positive drawing-off, apply the antistatic finish aqueous solution, obtain superhigh molecular weight polyethylene fibers;
Described antistatic finish is the mixture of Polyoxyethylene Ether antistatic additive and anionic antistatic agent, and described antistatic finish viscosity at 20 DEG C is 80mPas ~ 90mPas, and the mass concentration of the described antistatic finish aqueous solution is 0.5% ~ 3%.
First ultra-high molecular weight polyethylene spinning solution is made gelation preorientation strand by the embodiment of the present invention, and this process is well known to those skilled in the art, and specifically comprises:
Ultra-high molecular weight polyethylene spinning solution is sent into double screw extruder and carries out blending extrusion, obtain the first spinning solution;
Described first spinning solution is sent into spinning manifold, through drawing-off and fast cold curing, obtains gelation preorientation strand.
The present invention adopts ultra-high molecular weight polyethylene spinning solution, and this material mixes in double screw extruder, shearing, and this spinning solution refers to the solution will obtained in ultra-high molecular weight polyethylene powder dissolution to solvent well known to those skilled in the art.The higher spinning solution of solid content is used to be conducive to improving spinning efficiency, but along with the rising of spinning solution solid content, the spinning property of spinning solution can reduce, this just needs to improve strand extrusion temperature, and the degraded that the raising of strand extrusion temperature easily causes material even more serious, make the mechanical property of final obtained superhigh molecular weight polyethylene fibers reduce thus.For this reason, in the spinning solution adopted in this step operation of the present invention, the content of ultra-high molecular weight polyethylene is preferably 5wt% ~ 20wt%, is more preferably 6wt% ~ 15wt%, most preferably is 8wt% ~ 12wt%.
For the molecular weight of ultra-high molecular weight polyethylene, the weight average molecular weight of the ultra-high molecular weight polyethylene that the present invention adopts is preferably 3 ~ 5 × 10
6, the present invention more preferably adopts weight ratio to be the first ultra-high molecular weight polyethylene and second ultra-high molecular weight polyethylene of 3 ~ 8:1, and the weight average molecular weight of described first ultra-high molecular weight polyethylene is 4 ~ 5 × 10
6, the weight average molecular weight of the second ultra-high molecular weight polyethylene is 3 ~ 4 × 10
6.In addition, the ultra-high molecular weight polyethylene powder that the present invention uses the preferably distribution in Gaussian curve, particle diameter is preferably 60 order ~ 200 orders.
And the spin solvent in spinning solution is preferably cycloalkane: chain hydrocarbon isomers carries out the mixture be mixed to get according to the ratio of 85 ~ 90:10 ~ 15, the carbon atom number of described cycloalkane and alkane is preferably 25 ~ 50, is more preferably 30 ~ 40.Described spin solvent can use the spin solvent for ultra-high molecular weight polyethylene spinning solution well known to those skilled in the art, such as can use preferably less than 400 DEG C without gaseous volatilization, initial boiling point preferably higher than 450 DEG C, density is preferably 0.84g/cm
3~ 0.87g/cm
3flash-point is preferably higher than the white oil of 260 DEG C, be specifically as follows the one in mineral oil, paraffin oil and white oil, white oil can be 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, 100# white oil, 150# white oil.
The setting of the present invention to twin-screw extrusion is not particularly limited, and the inlet temperature preferably arranging extruder is 90 DEG C ~ 120 DEG C, and middle extrusion temperature is 240 DEG C ~ 280 DEG C, and outlet temperature is 280 DEG C ~ 350 DEG C, and screw speed is preferably 150r/min ~ 280r/min.Middle extruding one district ~ tetra-district temperature is preferably 240 DEG C ~ 250 DEG C, 250 DEG C ~ 270 DEG C, 250 DEG C ~ 270 DEG C, 270 DEG C ~ 280 DEG C successively.
After obtaining the first spinning solution, the embodiment of the present invention is sent in spinning manifold, through drawing-off and fast cold curing, obtains gelation preorientation strand.
During drawing-off, it is 8 ~ 30 times that the present invention preferably controls the first spinning solution at the drafting multiple of the spinning head of spinning manifold, is more preferably 8 ~ 12 times; The extrusion temperature of spinning manifold is preferably 285 DEG C ~ 320 DEG C.
After drawing-off, the embodiment of the present invention obtains the second spinning solution, and described second spinning solution just forms gelation preorientation strand through speed is cold after extruding from spinneret orifice.
In above-mentioned gel spinning technique, the aperture of spinneret orifice is preferably 0.8mm ~ 3mm, and the rate of extrusion that the draw ratio (L/D) of spinneret orifice is preferably the 8/1 ~ 20/1, second spinning solution is preferably set to 3m/min ~ 6m/min.It is fast cool time that second spinning solution is extruded into the time before falling into tank from spinneret orifice, and the second spinning solution is still in drawing-off state in fast cool time, and it is 0.05s ~ 2s that the present invention preferably controls fast cool time, and the cold temperature difference of speed is preferably 150 DEG C ~ 320 DEG C.
After obtaining gelation preorientation strand, the embodiment of the present invention is carried out balancing leaves standstill process, and strand, when standing, certain contraction can occur, and then effectively reduces original internal stress.Described balance leaves standstill and is treated to technological means well known to those skilled in the art, and dwell temperature is preferably 5 DEG C ~ 30 DEG C, and be more preferably 15 DEG C ~ 25 DEG C, time of repose is at least 12 hours.
Then, described balance is left standstill the gelation preorientation strand after process and carries out preliminary draft, extraction, drying and positive drawing-off successively by the embodiment of the present invention, and while positive drawing-off, apply the antistatic finish aqueous solution, obtains superhigh molecular weight polyethylene fibers.
After leaving standstill, gelation preorientation tow is carried out preliminary draft by the present invention, and described preliminary draft is process well known to those skilled in the art, and the drafting multiple of this process can be 2 ~ 6.
Leave standstill, need to select suitable solvent by the solvent extraction in gelation pre-oriented yarn out after preliminary draft, selected extractant reply solvent has good intermiscibility, should have lower boiling point and high volatility in addition.In the present invention, the extractant used in extraction process can be volatile lower paraffin hydrocarbon or halogenated hydrocarbons, as taken paraffin oil as solvent, selects industrial naptha to be extractant.
Carry out drying after being extracted by gelation pre-oriented yarn, volatilize to make extractant.In the present invention, the temperature of described drying is preferably 40 DEG C ~ 80 DEG C, is more preferably 50 DEG C ~ 70 DEG C, if this temperature is improper, can produce lousiness in follow-up positive drafting process, wet goods production process in impact; Described drying preferably includes first order drying and second level drying.In order to accelerate the volatilization of extractant, needing to apply certain tension force to frozen glue precursor when drying simultaneously, making precursor carry out drying under the state of tensioning, in the process, drafting multiple can be 1 ~ 3.Described leave standstill, extraction and drying be technological means well known to those skilled in the art, the present invention is not particularly limited.
Gelation pre-oriented yarn obtains precursor after extraction, drying, and then need to apply positive drawing-off to precursor, meanwhile, the present invention applies the antistatic finish aqueous solution, obtains superhigh molecular weight polyethylene fibers.
In the present invention, the temperature of described positive drawing-off is preferably 120 DEG C ~ 160 DEG C, and drafting multiple (abbreviation leads doubly) is preferably 5 ~ 15.Described hereinly lead the ratio doubly referring to the roller rotating speed of fiber after drawing machine drawing-off and roller rotating speed before; Positive drawing-off of the present invention refers to the drawing-off of leading and being doubly greater than 1 times.The present invention is not particularly limited the drawing-off general times that described gelation pre-oriented yarn bar applies in described preliminary draft, extraction, drying and positive drafting process, is preferably 30 ~ 55, is more preferably 40 ~ 55.
While the described positive drawing-off of applying, the present invention carries out the coating of the antistatic finish aqueous solution, makes antistatic finish directly be coated on fiber surface, avoids the loss of antistatic finish addition, thus makes the antistatic effect of fiber better.If add antistatic additive method by stoste, then antistatic additive is easily being decomposed through high temperature screw rod, is easily extracted when extraction tank extracts, and its basic loss is exhausted, DeGrain.
In the present invention, described antistatic finish is the mixture of Polyoxyethylene Ether antistatic additive and anionic antistatic agent, wherein, Polyoxyethylene Ether antistatic additive is main component, from antistatic property, it can reduce the triboelectrification amount of fiber surface on the one hand, can increase the hygroscopic capacity of fiber surface on the other hand, reduce surface resistivity, thus make electrostatic be easy to leak.In addition, Polyoxyethylene Ether antistatic additive also has the effects such as excellent lubrication and soft effect.The Polyoxyethylene Ether antistatic additive that the present invention can adopt comprises fatty alcohol-polyoxyethylene ether (AEO), alkylphenol polyoxyethylene (AQEO), aliphatic amine polyoxyethylene ether and fatty amide polyoxyethylene ether etc., be preferably fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene, be more preferably fatty alcohol-polyoxyethylene ether, wherein, for AEO, the effect of C12 and C13 is better, and the effect of EO 10 ~ 20 time is better; Surface-activity for AQEO, C8 ~ C9 is the strongest and heat resistance is better, and the effect of EO 10 ~ 20 time is also better.
And the active part of anionic antistatic agent mainly anion, as alkylsulfonate, alkyl sulfate and alkylphosphonic etc.; It can improve surface conductivity, rapid leak charge, thus reaches anlistatig effect.Described anionic antistatic agent is the antistatic additive that this area is commonly used, and is preferably alkylphosphonic, as surfactant LBH-400 etc.
In described antistatic finish, the ratio of the present invention to Polyoxyethylene Ether antistatic additive and anionic antistatic agent is not particularly limited, and described antistatic finish viscosity at 20 DEG C can be made to be 80mPas ~ 90mPas.The pH value of described antistatic finish is preferably 6.8 ~ 7.2, close to water.The present invention can adopt the trade mark of oil of SPC finish trial (demonstration) plant to be the finish of JDC, JE600, JDH, JP201 and JDH, and the trade mark that also can adopt Japanese this grease of bamboo company is the finish etc. of D583 and T2200.If adopt other composite finishes, viscosity is comparatively large, affects the mechanical property of finished fiber.Further, other finish usefulness are inadequate, if oil applying rate is low, then antistatic effect is bad, if oil applying rate is high, then the easy doubling of tow, stiff.
During coating, what the present invention adopted is the aqueous solution of described antistatic finish, and the mass concentration of the described antistatic finish aqueous solution is 0.5% ~ 3%.If the concentration of finish is excessive, not only product fiber number is had a significant effect, and cost is higher; If the concentration of finish is too small, then can not ensure that finished fiber has good antistatic behaviour.The present invention controls the mass concentration of the described antistatic finish aqueous solution in above-mentioned scope, be preferably 0.5% ~ 1%, be more preferably 0.6% ~ 0.8%, finished fiber can be made to have good antistatic behaviour and level and smooth, coherent, do not have a significant effect to product fiber number, cost is also lower simultaneously.
When allocating the described antistatic finish aqueous solution, the present invention preferably uses demineralized water, to form limpid solution, is beneficial to application, and the water namely in the described antistatic finish aqueous solution is preferably the soft water that hardness is less than 0.09 mM/l of alkaline earth ion concentration.
The present invention adopts Polyoxyethylene Ether antistatic additive and the composite antistatic finish of anionic antistatic agent, and control its viscosity, because the viscosity of described antistatic finish is very low, fine with the miscible effect of water, in solution, oil concentration is very low, and on fiber, oil content (OPU) is also very low, so while performance antistatic property, very little on the fiber number impact of fiber, substantially do not affect the mechanical property of fiber.Further, the permeability of described antistatic finish is very good, and can enter in fibre structure fast, have good attachment fastness, when downstream application, antistatic property exists for a long time.
The equipment such as positive drawing-off described herein is technological means well known to those skilled in the art, drawing roller i.e. the second drawing roller that the positive drawing-off of one-level will be adjacent after drawing roller adjacent before hot bellows i.e. the first drawing roller, hot bellows and hot bellows successively.The present invention preferably carries out the positive drawing-off of three grades to precursor, namely described positive drawing-off comprises the positive drawing-off of the first order, the positive drawing-off in the second level and the positive drawing-off of the third level.Further, the present invention preferably applies the antistatic finish aqueous solution before the hot bellows of the positive drawing-off in the second level after the first drawing roller of the positive drawing-off in the described second level.
The positive drawing-off of three grades of the present invention is specifically preferably: dried strand is carried out the positive drawing-off of the first order at 120 DEG C ~ 150 DEG C, then precursor is carried out the positive drawing-off in the second level at 130 DEG C ~ 160 DEG C, finally carries out the positive drawing-off of the third level at 140 DEG C ~ 160 DEG C.The drafting multiple that drafting multiple at different levels can adopt this area conventional, the present invention is not particularly limited.
For the concrete position that oils, in the positive drawing-off of described three grades, the present invention preferably applies the antistatic finish aqueous solution before the hot bellows of the positive drawing-off in the second level after the first drawing roller of the positive drawing-off in the described second level, by the heating of two baking ovens of the positive drawing-off in the second level below and the positive drawing-off of the third level, the moisture on tow can be dried, drying is carried out without the need to heating blower again, energy-saving and cost-reducing.Secondly; described antistatic finish temperature tolerance is better; after drawing-off by the larger multiple of the positive drawing-off of the first order; one can be avoided to lead the generation of large multiplying power chap, in addition, the extending uniform fold of finish is in tow surface; in two baking ovens of the positive drawing-off in the second level below and the positive drawing-off of the third level during drawing-off; easily fracture of wire place is occurring, the finish being coated on tow surface can play corresponding protective effect to tow, avoids the generation of lousiness.Moreover in positive drawing-off place of the first order, tow is less likely to occur heat most and leads fracture, make antistatic finish be coated on tow surface herein, the impact caused by lousiness is less, thus can ensure the stability of production.
If oiled in other position of positive drawing-off, effect can slightly decline, and as applied the antistatic finish aqueous solution after three lead baking oven and before finally leading roller, after easily occurring oiling, the situation such as dry not thoroughly, the winding curling round the roll of silk increases end breakage rate.
For concrete oiling method, the present invention preferably adopts oiling roller to apply the described antistatic finish aqueous solution, when there is fracture of wire in the positive drafting production line of speed, can not doubling curling round the roll, to guarantee production efficiency and product quality all more favourable.And if the oil nozzle of employing routine oils, when there is fracture of wire, doubling curling round the roll will bother very much, be unfavorable for producing; If oiled by oil groove, then OPU is too high, and effect is also not so good.
The present invention preferably adopts surface roughness Ra to be 0.3 ~ 1.5, is more preferably the oiling roller of 0.6 ~ 0.9, applies the described antistatic finish aqueous solution.For viscosity, very low and pH value is close to this antistatic finish of water, if adopt plain roller to apply, oiling roller surface is too smooth, when tow slips over from roller surface, due to finish can not evenly be attached to roller surface form rete and easily cause oil irregular; And the present invention preferably adopts the comparatively coarse oiling roller of surface smoothness to apply its aqueous solution, can make to oil more even, be beneficial to and obtain the good product of antistatic behaviour, but if oiling roller surface is too coarse, then can cause wearing and tearing to tow.
When the present invention applies the described antistatic finish aqueous solution, upper speed oil is preferably 15m/min ~ 25m/min, is more preferably 18m/min ~ 22m/min; Oil content (OPU) on gained superhigh molecular weight polyethylene fibers is preferably 1% ~ 5%, and be more preferably 2% ~ 4%, if oil content is too high, fibre number will obviously increase, and causes intensity to decline.
After positive drawing-off and the antistatic finish of coating complete, the embodiment of the present invention obtains superhigh molecular weight polyethylene fibers product.The present invention carries out the service checks such as electrostatic pressure test to products obtained therefrom, and wherein, the present invention adopts probing test instrument and SIMCO voltage instrument direct-on-line monitoring product electrostatic pressure, and readout units is kV.Test result shows, while guarantee product fiber number, and the electrostatic pressure < 0.2kV of described superhigh molecular weight polyethylene fibers, the qualified and odorlessness of mechanical property.
In addition, the tow of described superhigh molecular weight polyethylene fibers is more level and smooth, and coherent increases, and color and luster bleaches, brighten, and the broken end number produced due to doubling at winding portion reduces greatly.
Present invention also offers a kind of superhigh molecular weight polyethylene fibers prepared according to the method described above, the electrostatic pressure < 0.2kV of described superhigh molecular weight polyethylene fibers, be preferably 0.01kV ~ 0.1kV, the fiber number of described superhigh molecular weight polyethylene fibers can be 50D, 75D, 100D, 125D, 150D, 200D, 300D, 400D, 600D, 800D, 1200D and 1600D etc.The electrostatic pressure of superhigh molecular weight polyethylene fibers of the present invention is far below the electrostatic pressure of more than the 20kV of current superhigh molecular weight polyethylene fibers reality, therefore, superhigh molecular weight polyethylene fibers of the present invention has lower electrostatic, and tow collectivity is fine, is beneficial to application.
In order to understand the present invention further, below in conjunction with embodiment, superhigh molecular weight polyethylene fibers provided by the invention and preparation method thereof is specifically described.
In the examples below, the weight average molecular weight of the first ultra-high molecular weight polyethylene powder is 4.8 × 10
6, the weight average molecular weight of the second ultra-high molecular weight polyethylene powder is 3.2 × 10
6powder size is 80 order ~ 100 orders, solvent for use is 120# white oil, antistatic finish used is: the mixture of Polyoxyethylene Ether antistatic additive and anionic antistatic agent, liquid, clear, colorless, boiling point > 100 DEG C, at 20 DEG C, vapour pressure is 23mbar, and 20 DEG C of lower densities are 1.12g/cm
3, at 20 DEG C, pH value is that at 7,20 DEG C, viscosity is 85mPas, and this finish is with the soft water i.e. obtained antistatic finish aqueous solution.
Embodiment 1
1, in swelling still, add 88kg white oil and stir, 10kg first ultra-high molecular weight polyethylene powder and 2kg second supermolecule weight northylen powder is evenly added during stirring, mixing speed is 2500rpm, stirring is warming up to 105 DEG C, insulation 50min, obtain spinning solution, in spinning solution, the content of ultra-high molecular weight polyethylene is 12wt%.
2, spinning solution input double screw extruder step 1 obtained carries out shearing, blended and extrude, obtain the first spinning solution, the technological parameter of double screw extruder lists in table 1, and table 1 is the main spinning technology parameter of the embodiment of the present invention 1 ~ 4.
3, the first obtained for step 2 spinning solution is sent into spinning manifold, obtain the second spinning solution, spinning manifold technological parameter lists in table 1.
4, spinning solution spinning manifold extruded carry out 12 times drawing-off and in 0.5s speed cold 200 DEG C ~ 220 DEG C, obtain gelation preorientation tow (40).
5, the gelation preorientation tow obtained being received silk is placed in fiber barrel, at 25 DEG C, leave standstill 15 hours.
6, kerosene extraction is used after the gelation preorientation tow after standing process being carried out preliminary draft, then dry and 55 DEG C the second level of the first order respectively through 50 DEG C is dry, obtain protofilament bundle, the drafting multiple of above-mentioned preliminary draft, extraction and dry run lists in table 1.
7, protofilament Shu Jinhang tri-grades of positive drawing-offs of obtaining of step 6, draft process ginseng lists in table 1.And, after the first drawing roller of the positive drawing-off in the second level and before the hot bellows of the positive drawing-off in the second level, adopting through sand papering rear surface roughness is the oiling roller of 0.8, and coating concentration is the antistatic finish aqueous solution of 0.5%, obtains the 125D product of superhigh molecular weight polyethylene fibers.
According to method mentioned above, products obtained therefrom is carried out to the service checks such as electrostatic pressure test.Test result is see table 2, and table 2 is the main performance index of the superhigh molecular weight polyethylene fibers that the embodiment of the present invention 1 ~ 4 obtains.
Embodiment 2
In swelling still, add 92kg white oil and stir, 6kg first ultra-high molecular weight polyethylene powder and 2kg second supermolecule weight northylen powder is evenly added during stirring, mixing speed is 2500rpm, stirring is warming up to 105 DEG C, insulation 50min, obtain spinning solution, in spinning solution, the content of ultra-high molecular weight polyethylene is 8wt%.
Operation before three grades of positive drawing-offs is substantially the same manner as Example 1, and concrete technology parameter is see table 1.
By the protofilament Shu Jinhang tri-grades of positive drawing-offs obtained after drying, draft process ginseng lists in table 1.And, after the first drawing roller of the positive drawing-off in the second level and before the hot bellows of the positive drawing-off in the second level, adopting through sand papering rear surface roughness is the oiling roller of 0.8, and coating concentration is the antistatic finish aqueous solution of 1%, obtains the 150D product of superhigh molecular weight polyethylene fibers.
According to method mentioned above, products obtained therefrom is carried out to the service checks such as electrostatic pressure test.Test result is see table 2.
Embodiment 3
In swelling still, add 94kg white oil and stir, evenly add 6kg first ultra-high molecular weight polyethylene powder during stirring, mixing speed is 2500rpm, stirring is warming up to 105 DEG C, insulation 50min, obtain spinning solution, in spinning solution, the content of ultra-high molecular weight polyethylene is 6wt%.
Operation before three grades of positive drawing-offs is substantially the same manner as Example 1, and concrete technology parameter is see table 1.
By the protofilament Shu Jinhang tri-grades of positive drawing-offs obtained after drying, draft process ginseng lists in table 1.And, after the first drawing roller of the positive drawing-off in the second level and before the hot bellows of the positive drawing-off in the second level, adopting through sand papering rear surface roughness is the oiling roller of 0.8, and coating concentration is the antistatic finish aqueous solution of 1%, obtains the 200D product of superhigh molecular weight polyethylene fibers.
According to method mentioned above, products obtained therefrom is carried out to the service checks such as electrostatic pressure test.Test result is see table 2.
Embodiment 4
In swelling still, add 92kg white oil and stir, 6kg first ultra-high molecular weight polyethylene powder and 2kg second supermolecule weight northylen powder is evenly added during stirring, mixing speed is 2500rpm, stirring is warming up to 105 DEG C, insulation 50min, obtain spinning solution, in spinning solution, the content of ultra-high molecular weight polyethylene is 8wt%.
Operation before three grades of positive drawing-offs is substantially the same manner as Example 1, and concrete technology parameter is see table 1.
By the protofilament Shu Jinhang tri-grades of positive drawing-offs obtained after drying, draft process ginseng lists in table 1.And, after the first drawing roller of the positive drawing-off in the second level and before the hot bellows of the positive drawing-off in the second level, adopting through sand papering rear surface roughness is the oiling roller of 0.8, and coating concentration is the antistatic finish aqueous solution of 0.65%, obtains the 1600D product of superhigh molecular weight polyethylene fibers.
Comparative example 1
The content of the antistatic finish aqueous solution of removing coating, all the other operations are carried out according to embodiment 3, obtain the 200D primary products of superhigh molecular weight polyethylene fibers.
According to method mentioned above, products obtained therefrom is carried out to the service checks such as electrostatic pressure test.Test result is see table 2.
Comparative example 2
The content of the antistatic finish aqueous solution of removing coating, all the other operations are carried out according to embodiment 4, obtain the 1600D primary products of superhigh molecular weight polyethylene fibers.
According to method mentioned above, products obtained therefrom is carried out to the service checks such as electrostatic pressure test.Test result is see table 2.
The main spinning technology parameter of table 1 embodiment of the present invention 1 ~ 4
The fiber main performance index of table 2 embodiment of the present invention 1 ~ 4 and comparative example 1 ~ 2
From the above results, preparation method provided by the invention can make finished product polyethylene fiber while maintenance high strength, high-modulus, has lower electrostatic, is beneficial to application.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (6)
1. a preparation method for superhigh molecular weight polyethylene fibers, comprising:
A) ultra-high molecular weight polyethylene spinning solution is made gelation preorientation strand;
B) described gelation preorientation strand is carried out balance standing process;
C) described balance is left standstill the gelation preorientation strand after process and carry out preliminary draft, extraction, drying and positive drawing-off successively, and while positive drawing-off, apply the antistatic finish aqueous solution, described positive drawing-off comprises the positive drawing-off of the first order, the positive drawing-off in the second level and the positive drawing-off of the third level, after the first drawing roller of the positive drawing-off in the described second level, apply the antistatic finish aqueous solution before the hot bellows of the positive drawing-off in the second level; The described antistatic finish aqueous solution adopts oiling roller to apply, and obtains superhigh molecular weight polyethylene fibers;
The surface roughness Ra of described oiling roller is 0.3 ~ 1.5; Upper speed oil during described coating is 15m/min ~ 25m/min, and the oil content on gained superhigh molecular weight polyethylene fibers is 1% ~ 5%; Described antistatic finish is the mixture of Polyoxyethylene Ether antistatic additive and anionic antistatic agent, and described antistatic finish viscosity at 20 DEG C is 80mPas ~ 90mPas, and the mass concentration of the described antistatic finish aqueous solution is 0.5% ~ 3%.
2. preparation method according to claim 1, is characterized in that, the water in the described antistatic finish aqueous solution is the soft water that hardness is less than 0.09 mM/l of alkaline earth ion concentration.
3. preparation method according to claim 1, is characterized in that, the pH value of described antistatic finish is 6.8 ~ 7.2.
4. preparation method according to claim 1, is characterized in that, the drawing-off general times applied described gelation pre-oriented yarn bar in described preliminary draft, extraction, drying and positive drafting process is 30 ~ 55.
5. preparation method according to claim 4, is characterized in that, the temperature of the drying between described extraction and positive drawing-off is 40 DEG C ~ 80 DEG C.
6. a superhigh molecular weight polyethylene fibers, is characterized in that, is obtained by the preparation method described in any one of Claims 1 to 5, the electrostatic pressure < 0.2kV of described superhigh molecular weight polyethylene fibers.
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| CN106637487A (en) * | 2016-09-19 | 2017-05-10 | 华东理工大学 | Preparation method of novel middle/high-strength polyethylene fiber |
| CN106757467B (en) * | 2016-11-23 | 2021-07-30 | 上海斯瑞科技有限公司 | Ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN110117829A (en) * | 2019-05-07 | 2019-08-13 | 山东莱威新材料有限公司 | A method of ultra high molecular weight polyethylene fiber is extracted with dichloromethane |
| CN113151912B (en) * | 2021-05-10 | 2022-09-13 | 浙江理工大学上虞工业技术研究院有限公司 | A kind of ultra-high molecular weight polyethylene fiber and its preparation method and application |
| CN115752097A (en) * | 2022-11-30 | 2023-03-07 | 中硼科技(威海)有限公司 | Boron carbide bulletproof flashboard and preparation method thereof |
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