CN102776596B - Spinning swelling solution used for preparation of ultra-high molecular weight colored polyethylene fiber and spinning stock solution - Google Patents
Spinning swelling solution used for preparation of ultra-high molecular weight colored polyethylene fiber and spinning stock solution Download PDFInfo
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Abstract
The invention discloses a spinning swelling solution used for preparation of an ultra-high molecular weight colored polyethylene fiber. The spinning swelling solution comprises, by weight: 10-50% of ultra-high molecular weight polyethylene; a staining solution accounting for 0.01-10% of the weight of the ultra-high molecular weight polyethylene; and spinning solvents. In the invention, first, the staining solution is prepared into a swelling solution, in which the staining solution can be uniformly dispersed. Preparation of the staining solution into a spinning stock solution can be beneficial to uniform dispersion of the staining solution in the spinning stock solution. When using the spinning stock solution for gel spinning, after the spinning stock solution undergoes melting, dispersion, uniform mixing and unwrapping in a twin-screw extruder, the pigment particles in the staining solution can induce crystallization as a nucleating agent and form microcrystals. Extrusion molding of a crystal nucleus-containing spinning melt is in favor of obtaining nascent filaments characterized by low crystallinity and uniform crystal nucleus distribution. Thus, mechanical properties of the ultra-high molecular weight polyethylene fiber can be improved finally.
Description
Technical field
The present invention relates to superhigh molecular weight polyethylene fibers, be specifically related to a kind of spinning swelling solution for the preparation of ultra-high molecular weight polyethylene colored fibers and spinning solution.
Background technology
Ultra-high molecular weight polyethylene (UHMWPE) fiber, also claims high-strength high-modulus polyethylene fiber, refers to by the polyethylene of relative molecular weight more than 1,000,000 successively through high-performance fiber that spinning-extraction-drying-ultra-drawing is 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.
In the prior art, prepare superhigh molecular weight polyethylene fibers and usually use gel spinning technology, first this technology is invented by DSM N. V. of Holland.In gel spinning technology, the polyethylene of usual use relative molecular weight more than 1,000,000 is as raw material, using this raw material and the swelling suspension obtained of suitable solvent as spinning solution, then this spinning solution is twined through the shearing of screw extruder, even mixed, solution, obtain nascent gel fiber through spinning pack extrusion molding again, then nascent gel fiber is carried out follow-up extraction, drying and ultra-drawing and obtain superhigh molecular weight polyethylene fibers.
In prior art, the super high molecular polyethylene fiber precursor of preparation is substantially all white, but can need the finished product of shades of colour to meet customer need in the field such as such as rope, gloves, fishing line, kite string in downstream application.But because the internal organizational structure in superhigh molecular weight polyethylene fibers is stable fine and close hexagonal crystal system, main functional group is non-polar C-C straight chain, there is no other functional group, so effect is poor when the later stage paints to this off-white color precursor.Such as, when dyeing to fiber in the condition of High Temperature High Pressure, not only can destroy fibrous mechanical property, and cost is comparatively large, seriously polluted, be difficult to ensure that colouring is evenly; And for example, if painted to fiber by the method having coloring agent to apply, then cannot ensure permanent COLOR FASTNESS, in use fiber attrition, immersion all can produce degumming phenomenon.
Inorganic pigment is mixed in the spinning solution that 3,000,000 superhigh molecular weight polyethylene fibers powder make by Chinese patent CN101230499A, by the coloured gel fiber of twin-screw extrusion, then makes superhigh molecular weight polyethylene fibers through extraction, dry and hot gas spring.The inorganic pigment that particle diameter is larger is employed in above-mentioned patent, this inorganic pigment is difficult to be uniformly dispersed in spinning solution, therefore be difficult to form even nucleus and improve crystallization in spinning technique, though cause finished fiber to have color, but mechanical property is poor, only reach the intensity of 15 ~ 30g/d and the modulus of 400 ~ 1000g/d.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of spinning swelling solution for the preparation of ultra-high molecular weight polyethylene colored fibers and preparation method thereof; The present invention also provide a kind of utilize described spinning swelling solution to prepare spinning solution, utilize described spinning solution can prepare the ultra-high molecular weight polyethylene colored fibers with higher force performance.
In order to solve above technical problem, the invention provides a kind of spinning swelling solution for the preparation of ultra-high molecular weight polyethylene colored fibers, by weight, comprising:
Ultra-high molecular weight polyethylene 10 ~ 50%;
Account for the dyeing liquor of 0.01 ~ 10% of described ultra-high molecular weight polyethylene weight
Spin solvent.
Preferably, the content of the ultra-high molecular weight polyethylene in described spinning swelling solution is 15 ~ 40%.
Preferably, described dyeing liquor comprises dyeing solvent and pigment.
Preferably, described dyeing solvent is selected from one or more in isopropyl alcohol, ethanol, diethylene glycol, propylene glycol.
Preferably, comprising:
In first part of spin solvent, add ultra-high molecular weight polyethylene powder stir;
Second part of spin solvent is added and the first emulsified solvent obtains the first mixture in described first part of spin solvent;
Described first mixture is warming up to 90 DEG C ~ 130 DEG C insulations and swellingly obtains ultra-high molecular weight polyethylene swelling solution;
Described first emulsifying agent is formed through Over emulsfication by the 3rd part of spin solvent, antioxidant, dyeing liquor and surfactant;
First part of spin solvent: second part of spin solvent: the 3rd part of spin solvent: antioxidant: the weight ratio of surfactant is 45 ~ 55: 45 ~ 55: 1 ~ 20: 0.5 ~ 5: 0.05 ~ 0.1.
Preferably, described antioxidant comprises Ionization Potential of C-Centered Radicals agent for capturing, lactone stabilizer, organic phosphite, hindered phenol, thioether.
The present invention also provides a kind of preparation method of spinning solution of ultra-high molecular weight polyethylene fiber, comprising:
Get ultra-high molecular weight polyethylene lysate and the spinning swelling solution described in any one of Claims 1-4 is mixed to get according to the ratio that weight ratio is 0.42 ~ 2.85 spinning solution that ultra-high molecular weight polyethylene weight content is 10 ~ 15%;
The weight ratio of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene in described spinning swelling solution and described ultra-high molecular weight polyethylene lysate is 2.5 ~ 70.
Preferably, the weight ratio of described ultra-high molecular weight polyethylene lysate and described spinning swelling solution is 1.0 ~ 2.5.
Preferably, the weight ratio of the ultra-high molecular weight polyethylene in described spinning swelling solution and the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene lysate is 2.5 ~ 70.
Preferably, described superhigh molecular weight polyethylene fibers lysate is prepared as follows:
In the 4th part of spin solvent, add the second emulsified solvent, the 3rd emulsified solvent, the 4th emulsified solvent, the 5th part of spin solvent stir and obtain the second mixture, described second mixture is warming up to 100 DEG C ~ 190 DEG C stirrings and obtains ultra-high molecular weight polyethylene lysate;
Described second emulsified solvent by the 6th part of spin solvent and ultra-high molecular weight polyethylene according to 1 ~ 5: 0.4 ~ 0.6 ratio emulsification formed;
Described 4th emulsified solvent is formed through Over emulsfication by the 7th part of solvent, antioxidant;
Described 4th part of spin solvent: the 5th part of spin solvent: the 6th part of spin solvent: the weight ratio of the 7th part of spin solvent is 67 ~ 75: 15 ~ 25: 2 ~ 10: 2 ~ 4.
The present invention also provides a kind of spinning solution of the superhigh molecular weight polyethylene fibers obtained by above-mentioned preparation method.
The present invention also provides a kind of method preparing ultra-high molecular weight polyethylene colored fibers, comprising:
The spinning solution of the superhigh molecular weight polyethylene fibers utilizing technique scheme to prepare obtains ultra-high molecular weight polyethylene colored fibers through spinning, extraction, drying and ultra-drawing, and the multiple of described ultra-drawing is 30 times ~ 130 times.
The superhigh molecular weight polyethylene fibers that the present invention also provides the spinning solution described in a kind of basis to prepare
The invention provides a kind of spinning swelling solution for the preparation of superhigh molecular weight polyethylene fibers, dyeing liquor is first mixed with swelling solution by the present invention, and dyeing liquor can be dispersed in swelling solution.When the spinning solution using above-mentioned spinning swelling solution to prepare carries out gel spinning, spinning solution in double screw extruder after melting, dispersion, even mixed and solution twine, pigment particles in dyeing liquor can form crystallite as nucleator induced crystallization, during spinning melt extrusion molding with nucleus, be conducive to obtaining degree of crystallinity lower, the nascent strand that nucleus is evenly distributed, thus the final mechanical property improving superhigh molecular weight polyethylene fibers.
Present invention also offers a kind of preparation method of the spinning solution for the preparation of superhigh molecular weight polyethylene fibers, the present invention obtains by adding lysate mix and blend in above-mentioned swelling solution the spinning solution that ultra-high molecular weight polyethylene weight content is the high solids of 10-15%.Because lysate can play plasticization to swelling solution, therefore can reduce the viscosity of spinning solution system, ensure that spinning solution has good mobility and wire vent continuity, avoid occurring lousiness, fracture of wire in follow-up spinning process.In addition, by adding lysate in swelling solution, the ultrahigh molecular weight polyethylene gel strand produced during gel spinning can also be made to contain appropriate chain entanglement point, can ensure that the transmission that strand enables tension force in strand in follow-up drafting process is transmitted smoothly like this, to reach the object of ultra-drawing, prevent fracture of wire, ensure the stable of the performance of superhigh molecular weight polyethylene fibers.
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.
A kind of spinning swelling solution for the preparation of superhigh molecular weight polyethylene fibers of the present invention, with weight percentage, comprising:
Ultra-high molecular weight polyethylene 10% ~ 50%;
Dyeing liquor accounts for 0.01 ~ 10% of described ultra-high molecular weight polyethylene weight;
Spin solvent.
According to the present invention, described ultra-high molecular weight polyethylene swelling solution refer to well known to those skilled in the art ultra-high molecular weight polyethylene is mixed with spin solvent after, spin solvent Small molecular permeates, is diffused between the large molecule of ultra-high molecular weight polyethylene, the suspension obtained after the large molecule of ultra-high molecular weight polyethylene is expanded.Described spinning swelling solution is preferably prepared as follows, and specifically comprises:
In first part of spin solvent, add ultra-high molecular weight polyethylene powder stir;
Second part of spin solvent is added and the first emulsified solvent obtains the first mixture in described first part of spin solvent;
Described first mixture is warming up to 90 DEG C ~ 130 DEG C insulations and swellingly obtains ultra-high molecular weight polyethylene swelling solution;
Described first emulsified solvent is formed through Over emulsfication by the 3rd part of spin solvent, antioxidant, dyeing liquor and surfactant;
Described first part of spin solvent: second part of spin solvent: the 3rd part of spin solvent: antioxidant: surfactant is 45 ~ 55: 45 ~ 55: 1 ~ 20: 0.5 ~ 5: 0.05 ~ 0.1 according to weight ratio, be preferably 45 ~ 55: 45 ~ 55: 2 ~ 10: 1 ~ 3: 0.05 ~ 0.1, be more preferably 50: 50: 4 ~ 8: 1.5 ~ 2.5: 0.05 ~ 0.1.According to the present invention, described dyeing liquor accounts for 0.01% ~ 10% of the ultra-high molecular weight polyethylene weight in described swelling solution, is preferably 0.05% ~ 8%, is preferably 0.1% ~ 5%.
According to the present invention, described first part of emulsified solvent is preferably prepared as follows, antioxidant, dyeing liquor and surfactant are joined in the 3rd part of spin solvent and carry out stirring and emulsifying, mixing speed is preferably 2500rpm (turning per minute) ~ 3500rpm, be preferably 2750rpm ~ 3250rpm, mixing time is preferably 20min ~ 100min, is more preferably 30min ~ 80min, is more preferably 40min ~ 100min.
According to the present invention, when being carried out being incubated swelling by described first mixture, temperature retention time adjusts according to swellbility, preferably makes the swellbility of described super high molecular weight reach 1 ~ 2, is more preferably 1.1 ~ 1.8, is more preferably 1.2 ~ 1.6, then stops insulation.For temperature retention time, be preferably 30 ~ 100min, be more preferably 40 ~ 90min, be more preferably 50 ~ 80min.Swellbility η of the present invention calculates according to formula (I):
η=W
1/ W
2formula (I)
In formula (I), W
1implication be: get a ultra-high molecular weight polyethylene swelling solution, gained of weighing after 20min suction filtration; W
2implication be: be W by the described parts by weight obtained through suction filtration
1swollen materials decahydronaphthalene carry out three times extraction 90 DEG C dry to constant weight weigh gained.
According to the present invention, described dyeing liquor is made up of dyeing solvent and pigment, described dyeing solvent be selected from isopropyl alcohol, ethanol, diethylene glycol, propylene glycol one or more, described pigment is one or more in pigment blue 15, pigment black 7, pigment orange 5, pigment Green 7, described pigment particle size is preferably less than 500nm, be more preferably less than 400nm, be more preferably less than 300nm, be more preferably less than 150nm.For the ratio of fuel and dyeing solvent, can adjust according to the color of the final fiber needed.According to the present invention, can also add lubricant in described dyeing liquor, object lesson is as Disperbyk 191; Corrosion inhibitor, object lesson is as Hostacor LF20; Thickener, object lesson is as Rhodopol23; Defoamer, object lesson is as TegoAirex 901V.
The present invention also provides a kind of preparation method of spinning solution of ultra-high molecular weight polyethylene fiber, comprising:
Get ultra-high molecular weight polyethylene lysate and described ultra-high molecular weight polyethylene swelling solution is mixed to get according to the ratio that weight ratio is 0.42 ~ 2.85 spinning solution that ultra-high molecular weight polyethylene weight content is 10% ~ 15%;
The weight ratio of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution and described ultra-high molecular weight polyethylene lysate is 2.5 ~ 70.
Described ultra-high molecular weight polyethylene lysate refers to and well known to those skilled in the artly ultra-high molecular weight polyethylene is dissolved into the solution obtained in solvent.
According to the present invention, the weight content of the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution is preferably 11% ~ 49%, be more preferably 15% ~ 40%, the weight content most preferably being the ultra-high molecular weight polyethylene in ultra-high molecular weight polyethylene lysate described in 20% ~ 35% is preferably 0.2% ~ 5%, be more preferably 0.3% ~ 2.5%, be more preferably 0.8% ~ 2%.
According to the present invention, when described ultra-high molecular weight polyethylene swelling solution and described ultra-high molecular weight polyethylene lysate mix and blend are prepared spinning solution, the weight ratio of described ultra-high molecular weight polyethylene lysate and described ultra-high molecular weight polyethylene swelling solution is preferably 0.42-2.85, be more preferably 1.0 ~ 2.5, more preferably 1.4 ~ 1.8.The weight ratio of the ultra-high molecular weight polyethylene in described swelling solution and described lysate is preferably 2.5 ~ 70, is more preferably 5 ~ 50, is more preferably 10 ~ 30.For mixing time, be preferably 20min ~ 120min, be more preferably 45min ~ 100min, most preferably be 60min ~ 80min.
When described ultra-high molecular weight polyethylene swelling solution and described ultra-high molecular weight polyethylene lysate mix and blend are prepared spinning solution, preferably adopt following steps:
First ultra-high molecular weight polyethylene swelling solution is stirred under normal temperature and pressure in mixing kettle, then described ultra-high molecular weight polyethylene swelling solution is warming up to the temperature higher than swelling solution phase separation temperature, be preferably higher than phase separation temperature 8 DEG C ~ 15 DEG C, be more preferably higher than phase separation temperature 10 DEG C.The phase transition temperature of ultra-high molecular weight polyethylene belongs to and well known to a person skilled in the art general knowledge, different and different according to molecular weight, greatly between 70 DEG C ~ 90 DEG C.After swelling solution is warmed up to 65 ~ 85 DEG C by the present invention, then in described swelling solution, adds ultra-high molecular weight polyethylene lysate carry out being uniformly mixed obtaining spinning solution.
In the process of above-mentioned preparation mixing swelling solution and lysate, the object be warming up to by swelling solution higher than the temperature be separated reduces the viscosity of swelling solution, increases the mobility of swelling solution.Then in above-mentioned whipping process, the effect of lysate plays plasticization to swelling solution, the situation that the viscosity of spinning solution system is larger can be improved preferably, ensure that spinning solution has good mobility and wire vent continuity, avoid occurring lousiness, fracture of wire in follow-up spinning process.In addition, by adding lysate in swelling solution, the ultrahigh molecular weight polyethylene gel strand produced during gel spinning can also be made to contain appropriate entanglement, its objective is that the transmission that can enable to make tension force in strand in follow-up drafting process is carried out smoothly, to reach the object of follow-up ultra-drawing, prevent fracture of wire.
According to the present invention, when preparing described ultra-high molecular weight polyethylene lysate, preferably use following steps:
In the 4th spin solvent, add the second emulsified solvent, the 3rd emulsified solvent, the 5th part of spin solvent stir and obtain the second mixture, speed of agitator is preferably 2500rpm ~ 3500rpm, be more preferably 3000rpm, then described second mixture be warmed up to 100 DEG C ~ 190 DEG C stirrings and obtain ultra-high molecular weight polyethylene lysate.
Described second emulsified solvent by the 6th part of spin solvent and ultra-high molecular weight polyethylene according to 1 ~ 5: 0.4 ~ 0.6 ratio emulsification formed;
Described 3rd emulsified solvent is formed through Over emulsfication by the 7th part of spin solvent, antioxidant, and described 7th part of spin solvent preferably accounts for 2% ~ 4% of the solvent total amount in described ultra-high molecular weight polyethylene lysate by weight.In the process preparing ultra-high molecular weight polyethylene lysate, described 4th part of spin solvent: described 5th part of spin solvent: the 6th part of spin solvent: the 7th part of spin solvent is 67 ~ 75: 15 ~ 25: 2 ~ 10: 2 ~ 4 according to weight ratio, be more preferably 67 ~ 75: 15 ~ 25: 3 ~ 8: 2 ~ 4, be more preferably 67 ~ 75: 20: 4 ~ 6: 3.
According to the present invention, when preparing described second emulsified solvent, described 6th part of spin solvent and ultra-high molecular weight polyethylene can be divided into two parts uniformly and carry out emulsification respectively, emulsification times is preferably 10min ~ 60min, be preferably 20min ~ 50min, be more preferably 30min ~ 40min.
Described second mixture is warmed up to 100 DEG C ~ 190 DEG C stirrings to obtain ultra-high molecular weight polyethylene lysate and preferably use following steps: first described second mixture is warming up to 100 DEG C ~ 150 DEG C, preferably to 120 DEG C ~ 140 DEG C carries out stirring at low speed, stirring at low speed speed is preferably 17rpm ~ 25rpm, is more preferably 18rpm ~ 20rpm; The temperature being stirred to the second mixture preferably reaches 140 DEG C ~ 190 DEG C, more preferably 150 DEG C ~ 180 DEG C are reached, then rotating speed brought up to 35rpm ~ 45rpm, more preferably bring up to 38rpm ~ 42rpm and carry out high-speed stirred, carry out insulation again and obtain ultra-high molecular weight polyethylene lysate, temperature retention time is preferably 30min ~ 100min, is more preferably 40min ~ 80min.
In the process preparing ultra-high molecular weight polyethylene lysate, second mixture is first heated and carries out stirring at low speed, its objective is heating and stirring at low speed process in, ultra-high molecular weight polyethylene feed particles complete swelling also has major part to start to dissolve, entanglement between the high polymer macromolecular chain now in ultra-high molecular weight polyethylene is eliminated substantially, makes nucleator can enter solution and twines between strand and carry out preliminary dispersion.The temperature of stirring at low speed to the second mixture reaches 120 DEG C ~ 190 DEG C, carries out high-speed stirred after preferably reaching 150 DEG C ~ 180 DEG C, its objective is and promotes that the dissolving of ultra-high molecular weight polyethylene and nucleator disperse more uniformly.
According to the present invention, described antioxidant comprises the composite antioxidant mixed by Ionization Potential of C-Centered Radicals agent for capturing, lactone stabilizer, organic phosphite, hindered phenol and thioether.The amount of described antioxidant accounts for 1 ~ 8% of the ultra-high molecular weight polyethylene weight in described spinning solution of ultra-high molecular weight polyethylene fiber, is preferably 2 ~ 7%, is more preferably 4 ~ 6%.Antioxidant can distribute according to the weight uniformity of the ultra-high molecular weight polyethylene in spinning swelling solution and lysate.
Spin solvent used herein is preferably cycloalkane: chain hydrocarbon isomers carries out according to the ratio of 85 ~ 90: 10 ~ 15 mixture that is mixed to get, and 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 0.84 ~ 0.87g/cm
3, flash-point is preferably higher than the white oil of 260 DEG C.The white oil that the present invention uses 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
Surfactant of the present invention can be anion surfactant well known to those skilled in the art, cationic surfactant, non-ionic surface active agent, object lesson can be stearic acid, neopelex, quaternary ammonium compound, fatty glyceride, aliphatic acid sorb smooth (sapn), polysorbate (tween) etc., but is not limited thereto.
The weight average molecular weight M of ultra-high molecular weight polyethylene used in the present invention
wbe preferably 3 ~ 5 × 10
6, be more preferably 3.5 ~ 4.5 × 10
6, the non-linear rate < 5% of ultra-high molecular weight polyethylene; The present invention preferably uses particle diameter to be the ultra-high molecular weight polyethylene powder of Gaussian Profile, and the particle diameter of described powder is preferably 60 order ~ 200 orders.
According to the present invention, the superhigh molecular weight polyethylene fibers spinning solution prepared can prepare superhigh molecular weight polyethylene fibers according to gel spinning technology well known to those skilled in the art, object lesson can be: spinning solution is sent into double screw extruder and carry out solution and twine, the inlet temperature of double screw extruder is preferably 85 DEG C ~ 120 DEG C, middle extrusion temperature is 240 DEG C ~ 280 DEG C, and outlet temperature is 280 DEG C ~ 320 DEG C.The optimal process of gel spinning is: the aperture of spinneret orifice is 0.6mm ~ 5mm, and the draw ratio L/D of spinneret orifice is 6/1 ~ 30/1, and spinning solution rate of extrusion is 0.5m/min ~ 10m/min; After extruding, spinneret draft ratio controls between 5 ~ 20 times, and preferably between 6 ~ 15 times, spinning solution obtains frozen glue strand through the cooling and shaping of 0 DEG C ~ 36 DEG C.
After obtaining frozen glue strand, extracted by frozen glue strand, extractant is preferably hexane, heptane, toluene, chloromethanes, solvent naphtha, kerosene, is more preferably kerosene.Then the strand after extraction is carried out drying, baking temperature is preferably 40 DEG C ~ 80 DEG C, then dry strand is applied 30 times ~ 130 times in the temperature range of 70 DEG C ~ 160 DEG C, and preferred 40-60 hot gas spring doubly makes superhigh molecular weight polyethylene fibers.When carrying out hot gas spring to described dried strand, that preferably carries out at least two-stage to described strand just leads hot gas spring doubly, and the temperature of first order hot gas spring is preferably 120 DEG C ~ 160 DEG C, leads and is doubly preferably 2 times ~ 10 times, be more preferably 5 times ~ 10 times; The temperature of second level hot gas spring is preferably 130 DEG C ~ 160 DEG C, leads and is doubly preferably 2 times ~ 10 times, be more preferably 5 times ~ 10 times.Carry out after two-stage just leading hot gas spring doubly, can also carry out the negative drawing-off of one-level to strand, negative drawing temperature is preferably 120 DEG C ~ 140 DEG C, leads and is doubly preferably 0.91 times ~ 0.99 times.
The invention provides a kind of spinning swelling solution for the preparation of superhigh molecular weight polyethylene fibers, dyeing liquor is first mixed with swelling solution by the present invention, and dyeing liquor can be dispersed in swelling solution.After using above-mentioned dyeing liquor to be configured to spinning swelling solution, be conducive to dyeing liquor dispersed in spinning swelling solution.When the spinning solution using above-mentioned spinning swelling solution to prepare carries out gel spinning, spinning solution in double screw extruder after melting, dispersion, even mixed and solution twine, pigment particles in dyeing liquor can form crystallite as nucleator induced crystallization, during spinning melt extrusion molding with nucleus, be conducive to obtaining degree of crystallinity lower, the nascent strand that nucleus is evenly distributed, thus the final mechanical property improving superhigh molecular weight polyethylene fibers.
In the present invention, fibrous mechanical property tests according to GB/T19975-2005.
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 the restriction to the claims in the present invention scope.
In order to better comparative effectiveness, in following embodiment and comparative example, employ identical raw material, the weight average molecular weight M of ultra high molecular polyethylene used
wbe 4.2 × 10
6, powder size is 80 μm ~ 120 μm, solvent for use 120# white oil, and pigment used is Switzerland's vapour bar pigment.
The nucleator used in following examples and comparative example, antioxidant, surfactant, coloring agent are as table 1:
The raw material that table 1 embodiment of the present invention uses
Embodiment 1
Ultra-high molecular weight polyethylene colored fibers is prepared according to following operation:
The polyethylene colored swelling solution of operation 1, preparing super molecular weight;
Operation 2, preparing super molecular weight polyethylene lysate;
Operation 3, the coloured stoste of preparing super molecular weight polyethylene spinning;
Operation 4, spinning.
Operation 1 specifically comprises the steps:
Step 11
Get 50kg first part of white oil being placed in swelling still and stir, during stirring, evenly spray into the ultra-high molecular weight polyethylene powder of 30kg;
Step 12
Get the 3rd part of white oil of 4kg, then add 0.05kg antioxidant, the neopelex surfactant of 0.06kg carries out emulsification stirring and emulsifying and obtain the first emulsified solvent, wherein mixing speed is 3000rpm, and emulsification times is 40min;
Step 13
Second part of white oil of the first emulsified solvent and 50kg is put in described swelling still, stirring is warming up to 105 DEG C, temperature retention time is 50min, and obtain the ultra-high molecular weight polyethylene swelling solution that swellbility is 1.23, in this swelling solution, the weight ratio of ultra-high molecular weight polyethylene is 22%.
First part of white oil in swelling solution: second part of white oil: the 3rd part of white oil is 52: 48: 4 by weight.
Operation 2 specifically comprises the steps:
Step 21
Get the ultra high molecular polyethylene powder of 4kg the 6th part of white oil and 1.1kg, described 6th part of white oil and polyethylene powders are divided into uniformly two parts and carry out emulsification and obtain the second emulsifying agent, emulsification times is 30min, and mixing speed during emulsification is 3000rpm;
Step 22
Get 3kg the 7th part of white oil, interpolation 2,6-tri-grades of butyl-4-methylphenol antioxidant of 0.04kg, the talcum powder of 0.05kg carry out emulsification and obtain the 3rd emulsifying agent, and mixing speed during emulsification is 3000rpm, and emulsification times is 40min;
Step 23
The 4th part of white oil getting 67kg is placed in dissolution kettle and stirs, in dissolution kettle, then put into the 5th part of white oil mixing of the second emulsifying agent, the 3rd emulsifying agent, 20kg;
Step 24
Compound step 23 obtained is warming up to 130 DEG C and stirs, and mixing speed is 19rpm;
Step 25
Heated up by the compound of step 24 after reaching 160 DEG C, stir with the speed of 40rpm, then start insulation, temperature retention time is obtain ultra-high molecular weight polyethylene lysate after 50min.
Operation 3 specifically comprises the steps:
Step 3
Get swelling solution stirring at normal temperature in swelling still prepared by operation 1, and then swelling solution is warmed up to 90 DEG C, the lysate mix and blend 70min dropping into operation 2 preparation again in swelling solution obtains spinning solution of ultra-high molecular weight polyethylene fiber, and wherein swelling solution and lysate weight ratio are 1: 1.1.
Operation 4 specifically comprises the steps:
Step 41
Spinning solution is sent in double screw extruder and carry out macromolecular solution and twine.Wherein, double screw extruder send that inlet temperature is 100 DEG C, medium temperature is 260 DEG C, outlet temperature is 290 DEG C;
Step 42
Suspension twines through the solution of double screw extruder, extrude and make transparent frozen glue solution.Frozen glue solution to be extruded with the plastic-blasting speed of 1m/min through measuring pump, the spinnerets (orifice diameter 1mm, draw ratio is L/D is 10/1) with 400 holes to enter temperature be that the tank that solidifies of 25 DEG C makes strand shape to obtain gel fiber;
Step 43
The gel fiber obtained is adopted kerosene extraction, and dry and 60 DEG C the second level of the first order then respectively through 55 DEG C is dry;
Step 44
Dried gel fiber is carried out the positive drawing-off of two-stage successively, and one-level bears drawing-off, and concrete technology is: first order drawing temperature is 100 DEG C, and leading is doubly 6.7 times; Second level drawing temperature is 120 DEG C, and leading is doubly 8.9 times; Third level drawing temperature is 130 DEG C, and leading is doubly 0.9 times.
The indices of spinning solution and the mechanical property of fiber the results are shown in table 4.
Embodiment 2-embodiment 9
Above-mentioned 8 implement technological parameter refer to table 2 and table 3, parameter unlisted in table 2 with table 3 is identical with embodiment 1.
The indices of spinning solution and the mechanical property of fiber the results are shown in table 4 and table 5.
Comparative example 1
Get ultra-high molecular weight polyethylene and the 93kg white oil of 7kg, add 2 of 1.5kg, the neopelex surfactant of dyeing liquor I, 0.014kg of 6-tri-grades of butyl-4-methylphenol antioxidant, 0.35kg in first swelling still 65 DEG C stir 24 hours, then put into second swelling still 75 DEG C to stir 12 hours, then put into the 3rd swelling still 110 DEG C to stir 12 hours, the mixing speed of above-mentioned three swelling stills is 5rpm, finally force to be cooled to 70 DEG C, obtain the spinning solution that solid content is about 7%.
Spinning technology parameter is identical with embodiment 1.
The indices of spinning solution and the mechanical property of fiber the results are shown in table 5.
Comparative example 2
According to the preparation technology of comparative example 1 prepare ultra-high molecular weight polyethylene content be the swelling solution of 11% as spinning solution, other parameter is identical with comparative example 1.
Spinning technology parameter is identical with embodiment 2.
The indices of spinning solution and the mechanical property of fiber the results are shown in table 5.
The technological parameter of the spinning solution of table 2 embodiment 2-5
The technological parameter of the spinning solution of table 3 embodiment 6-9
The spinning solution index of table 4 embodiment 1-5 and the performance of fiber
The spinning solution index of table 5 embodiment 7-9, comparative example 1-3 and the performance of fiber
From the comparing result of table 4 and table 5, compared with not adding the spinning solution of nucleator, pigment particles in the present invention in dyeing liquor can form crystallite as nucleator induced crystallization, during spinning melt extrusion molding with nucleus, be conducive to obtaining degree of crystallinity lower, the nascent strand that nucleus is evenly distributed, the ultra-high molecular weight polyethylene colored fibers intensity prepared under therefore identical spinning condition significantly improves, CV value is low, and stability of fiber is good.
Above spinning solution of ultra-high molecular weight polyethylene fiber provided by the present invention and preparation method thereof is described in detail.Apply specific case herein to set forth principle of the present invention and embodiment, 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 (13)
1. for the preparation of a spinning swelling solution for ultra-high molecular weight polyethylene colored fibers, it is characterized in that, prepare in accordance with the following methods:
In first part of spin solvent, add ultra-high molecular weight polyethylene powder stir;
Second part of spin solvent is added and the first emulsified solvent obtains the first mixture in described first part of spin solvent;
Described first mixture is warming up to 90 DEG C ~ 130 DEG C insulations and swellingly obtains ultra-high molecular weight polyethylene swelling solution;
Described first emulsified solvent is formed through Over emulsfication by the 3rd part of spin solvent, antioxidant, dyeing liquor and surfactant;
First part of spin solvent: second part of spin solvent: the 3rd part of spin solvent: antioxidant: the weight ratio of surfactant is 45 ~ 55:45 ~ 55:1 ~ 20:0.5 ~ 5:0.05 ~ 0.1;
Described spinning swelling solution, with weight percentage, comprising:
Ultra-high molecular weight polyethylene 10% ~ 50%;
Account for the dyeing liquor of 0.01 ~ 10% of described ultra-high molecular weight polyethylene weight;
Spin solvent.
2. spinning swelling solution according to claim 1, is characterized in that, the content of the ultra-high molecular weight polyethylene in described spinning swelling solution is 15 ~ 40%.
3. spinning swelling solution according to claim 1, is characterized in that, the dyeing liquor in described first emulsified solvent comprises dyeing solvent and pigment.
4. spinning swelling solution according to claim 3, is characterized in that, described dyeing solvent be selected from isopropyl alcohol, ethanol, diethylene glycol, propylene glycol one or more.
5. the preparation method of the spinning swelling solution described in any one of Claims 1-4, is characterized in that, comprising:
In first part of spin solvent, add ultra-high molecular weight polyethylene powder stir;
Second part of spin solvent is added and the first emulsified solvent obtains the first mixture in described first part of spin solvent;
Described first mixture is warming up to 90 DEG C ~ 130 DEG C insulations and swellingly obtains ultra-high molecular weight polyethylene swelling solution;
Described first emulsified solvent is formed through Over emulsfication by the 3rd part of spin solvent, antioxidant, dyeing liquor and surfactant;
First part of spin solvent: second part of spin solvent: the 3rd part of spin solvent: antioxidant: the weight ratio of surfactant is 45 ~ 55:45 ~ 55:1 ~ 20:0.5 ~ 5:0.05 ~ 0.1.
6. preparation method according to claim 5, is characterized in that, described antioxidant comprises Ionization Potential of C-Centered Radicals agent for capturing, lactone stabilizer, organic phosphite, hindered phenol, thioether.
7. a preparation method for spinning solution of ultra-high molecular weight polyethylene fiber, is characterized in that, comprising:
Get ultra-high molecular weight polyethylene lysate and the spinning swelling solution described in any one of Claims 1-4 is mixed to get according to the ratio that weight ratio is 0.42 ~ 2.85 spinning solution that ultra-high molecular weight polyethylene weight content is 10 ~ 15%;
The weight ratio of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene in described spinning swelling solution and described ultra-high molecular weight polyethylene lysate is 2.5 ~ 70.
8. preparation method according to claim 7, is characterized in that, the weight ratio of described ultra-high molecular weight polyethylene lysate and described spinning swelling solution is 1.0 ~ 2.5.
9. preparation method according to claim 8, is characterized in that, the weight ratio of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene in described spinning swelling solution and described ultra-high molecular weight polyethylene lysate is 2.5 ~ 70.
10. preparation method according to claim 9, is characterized in that, described superhigh molecular weight polyethylene fibers lysate is prepared as follows:
In the 4th part of spin solvent, add the second emulsified solvent, the 3rd emulsified solvent, the 5th part of spin solvent stir and obtain the second mixture, described second mixture is warming up to 100 DEG C ~ 190 DEG C stirrings and obtains ultra-high molecular weight polyethylene lysate;
Described second emulsified solvent is formed according to the ratio emulsification of 1 ~ 5:0.4 ~ 0.6 by the 6th part of spin solvent and ultra-high molecular weight polyethylene;
Described 3rd emulsified solvent is formed through Over emulsfication by the 7th part of solvent, antioxidant;
Described 4th part of spin solvent: the 5th part of spin solvent: the 6th part of spin solvent: the weight ratio of the 7th part of spin solvent is 67 ~ 75:15 ~ 25:2 ~ 10:2 ~ 4.
The spinning solution of 11. superhigh molecular weight polyethylene fibers obtained by the preparation method described in any one of claim 7 to 10.
12. 1 kinds of methods preparing ultra-high molecular weight polyethylene colored fibers, is characterized in that, comprising:
Utilize the spinning solution described in claim 11 to obtain ultra-high molecular weight polyethylene colored fibers through spinning, extraction, drying and ultra-drawing, the multiple of described ultra-drawing is 30 times ~ 130 times.
The superhigh molecular weight polyethylene fibers that 13. spinning solutions according to claim 11 prepare.
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| CN103074786B (en) * | 2012-12-20 | 2014-11-05 | 绍兴金渔纺织新技术有限公司 | Ultrahigh molecular weight polyethylene fiber dyeing method |
| CN103046403B (en) * | 2012-12-20 | 2014-10-29 | 绍兴金渔纺织新技术有限公司 | Method for preparing colored UHMW (ultra-high molecular weight) polyethylene fibers |
| CN103015233B (en) * | 2012-12-20 | 2015-01-28 | 绍兴金渔纺织新技术有限公司 | Process for dyeing ultra-high molecular weight polyethylene fibers |
| CN103590128B (en) * | 2013-11-05 | 2016-06-08 | 东华大学 | A kind of preparation method of coloured ultrahigh relative molecular weight polyethylene fiber |
| CN103866416B (en) * | 2014-03-20 | 2016-02-10 | 剑乔科技江苏有限公司 | A kind of preparation method of ultra-high molecular weight polyethylene colored fibers |
| CN105133066B (en) * | 2014-05-28 | 2017-08-18 | 杭州翔盛高强纤维材料股份有限公司 | A kind of preparation method of ultra-high molecular weight polyethylene colored fibers |
| CN106544746A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | Ultra-high molecular weight polyethylene mixed solution dry spinning prepares the method and fiber of colored fibre |
| CN106567152A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Colored ultrahigh molecular weight polyethylene fiber and production method thereof |
| CN105386135A (en) * | 2015-10-16 | 2016-03-09 | 天津工业大学 | Electrostatic spinning solution for producing polytetrafluoroethylene ultrafine fiber microporous membrane |
| CN106245136B (en) * | 2016-08-17 | 2019-03-29 | 东华大学 | A kind of coloured ultra high molecular weight polyethylene fiber and preparation method thereof |
| CN116356443A (en) * | 2023-02-01 | 2023-06-30 | 南通恒尚新材料科技有限公司 | Coloring color paste for ultra-high molecular weight polyethylene fibers and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101122051A (en) * | 2007-09-24 | 2008-02-13 | 湖南中泰特种装备有限责任公司 | Method for preparing low-titer high-strength high-modulus polyethylene fibre |
| CN101886295A (en) * | 2009-05-11 | 2010-11-17 | 胡盼盼 | Ultra-high molecular weight polyethylene colored fibers and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101122051A (en) * | 2007-09-24 | 2008-02-13 | 湖南中泰特种装备有限责任公司 | Method for preparing low-titer high-strength high-modulus polyethylene fibre |
| CN101886295A (en) * | 2009-05-11 | 2010-11-17 | 胡盼盼 | Ultra-high molecular weight polyethylene colored fibers and preparation method thereof |
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| Title |
|---|
| JP特表2009-513743A 2009.04.02 * |
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