CN102041557B - Production method of high-intensity and high-modulus polyethylene fibers - Google Patents
Production method of high-intensity and high-modulus polyethylene fibers Download PDFInfo
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Abstract
The invention discloses a production method of high-intensity and high-modulus polyethylene fibers. The method comprises a swelling and dissolving step, a filtering step, a spinning step, a refrigerating and solidifying step, a pre-stretching step, an extracting step, a drying step, an ultra-stretching step and a winding step, wherein the swelling and dissolving step is performed in a kneading machine; and transparent and uniform spinning solution obtained in the swelling and dissolving step is quantitatively fed into a single screw extruder with stirring for extruding. The production method has the advantages of simple preparation method and high yield of over 300 tons/year and is easy to operate.
Description
Technical field
The present invention relates to a kind of production method of polyethylene fiber, be specifically related to a kind of quick dissolving ultra-high molecular weight polyethylene (UHMWPE), to realize the high production capacity production method of high-strength and high-modulus polyethylene fiber.
Background technology
High-strength high-modulus polyethylene fiber is take ultra-high molecular weight polyethylene (UHMWPE) as raw material, make through gel spinning, a super times drawing-off, original large molecule of polyethylene that is lack of alignment that mutually is wound around is twined by dissolving suitable solution, ultra-drawing reaches the high degree of orientation and degree of crystallinity again, thereby makes fiber have the premium properties such as light weight, softness, Gao Mo, UV resistant, shock-resistant, acid and alkali-resistance, seawater corrosion resistance.
1979, Dutch DSM N. V. applied for adopting the frozen glue technology to make the patent (NL7900990, NL7904990 and corresponding US4344908, examined patent publication 64-8732, US4422993) of superhigh molecular weight polyethylene fibers.The frozen glue technology refers to polyethylene and suitable solvent are made spinning solution, then spinning solution is cooled to gel state, adopts extraction process with removal of solvents, then obtains polyethylene fiber through super-dry, super doubly (30 times～130 a times) hot-stretch.Because the gel spinning method is conducive to form the more Shen backbone of high efficiency of transmission tension load, the polyethylene fiber of therefore preparing has very high strength and modulus, and impact resistance is excellent, uses more extensive.
The key technology of polyethylene gel spinning is that the even super high molecular polyethylene solution that tangles between large molecule is removed in preparation.If solution is not uniformly, in the whole process of preparation fiber, quality and the draftability when gel state of nascent strand will be seriously influenced, and the final mechanical property of material also can be subject to more serious infringement.Yet making polythene uniform solution is a very complicated process, and this is because ultra-high molecular weight polyethylene has very high weight average molecular weight (5 * 10
5Above), adopt in the autoclave whipping process at polyethylene solution, the large molecule of polyethylene often be gathered in puddler or other device around, usually said Weissenberg effect (weissenberkg phenomenon) namely occurs.When Weissenberg effect occurs, be difficult to the uniform spinning solution of preparation.
In order to solve the uniform dissolution of ultra-high molecular weight polyethylene, people have invented and will adopt the further polyethylene dissolving of double screw extruder to prepare the method for homogeneous solution after the ultra-high molecular weight polyethylene swelling.CN1190137C, CN1047414C, JP.86-73743, JP86-143439 all disclose first ultra-high molecular weight polyethylene has been fed through after preliminary swelling the technical scheme that double screw extruder dissolves quantitatively in solvents.The effect of mixing due to the brilliance of double screw extruder, greatly improved solute effect, ultra-high molecular weight polyethylene solubilized concentration is greatly enhanced, and full-bodied solution has been created condition for foundation, the deaeration of double screw extruder head pressure afterwards again.
The process that adopts double screw extruder to prepare the super high molecular weight spinning solution can be divided into two stages: the swelling of polyethylene fiber in solvent and the dissolving in double screw extruder.In the swelling stage, main manifestations is that solvent permeates in diffusion in ultra-high molecular weight polyethylene, the polyethylene volumetric expansion.Swelling is an endothermic process very responsive to temperature, only carries out in very narrow temperature range, and improper causing of swelling can't make uniform spinning solution.If swelling is not enough, " half-cooked " phenomenon appears, and the dissolving of ultra-high molecular weight polyethylene will be inhomogeneous; Swelling is too abundant, and Ultra high molecular weight polyethylene particles can the group of being gathered into, and hinders the normal evenly feeding of double screw extruder, and suitable swelling becomes the key of preparation homogeneous solution.
If the superhigh molecular weight polyethylene fibers spinning solution that the preparation material is inhomogeneous, can cause nascent strand performance inhomogeneous when spinning, the inhomogeneous nascent strand of performance is in particular in the coefficient of dispersion (coefficient of variation of the various mechanical properties of fiber through preparing the polyethylene fiber of unstable properties after extraction-super drawing.The CV value) larger.More seriously, use inhomogeneous ultra-high molecular weight polyethylene spinning solution to carry out spinning and also the phenomenon of fracture of wire can occur easily.
In addition, in dissolution phase, usually requiring the time of staying of spinning solution in double screw extruder is 0.3D minute, and D is screw diameter.The higher screw diameter of output is larger, and the time of staying requires longer, if will improve output to 300 ton/year, the flow of spinning solution will reach 6.25kg/min, and spinning solution density will reach 0.93kg/L, and the twin-screw diameter is greater than 135MM and just can meets the demands.Be the double screw extruder of 135MM and adopt screw diameter, time of stopping in double screw extruder of spinning solution is 40.5 minutes, if the time of staying was lower than 40.5 minutes, polyethylene just can not uniform dissolution, and at present the screw diameter of double screw extruder is greater than 135MM, and its draw ratio can only 46, is no more than 52, therefore be subjected to the restriction of equipment, existing double screw extruder can't be realized step dissolving, the purpose that mixes.Therefore also just limited the raising of output.Reach ultra-high molecular weight polyethylene more than 3,000,000 for molecular weight in addition, if the time of staying is oversize in double screw extruder, add up cut shear large, be very easy to cause the degraded of ultra-high molecular weight polyethylene, thereby have influence on the performance of final fiber.
Therefore, need a kind of method that can prepare uniform superhigh molecular weight polyethylene fibers spinning solution, with scale produce high-strength high-modulus polyethylene fiber.
Summary of the invention
The present invention is exactly in order to address the above problem, and overcomes the deficiencies in the prior art, provides a kind of high production capacity production method of high-strength high-modulus polyethylene fiber, to realize the large-scale production of polyethylene fiber.
In order to realize the foregoing invention purpose, the technical solution adopted in the present invention is:
A kind of production method of high-strength high-modulus polyethylene fiber, comprise swelling dissolving step, filtration step, spray silk step, cryocoagulation step, predraft step, extraction step, drying steps, ultra-drawing step, coiling step, it is characterized in that, described swelling dissolving step carries out in a kneader, and the transparent homogeneous spinning solution that process swelling dissolving step obtains quantitatively feeds spinning solution in single screw extrusion machine while stirring to be extruded.
In described swelling dissolving step, ultra-high molecular weight polyethylene powder and white oil are 4-50% according to the white proportion by subtraction of nominal weight concentration.
Described swelling dissolving step carries out under nitrogen protection.
Kneader of the present invention is the kneader with the two kneading blades that drive separately by two motors.
Kneader of the present invention changes shear rate by respectively a kneading blade being carried out speed governing separately.
Swelling dissolving step of the present invention is divided into dispersion steps, swelling step and dissolving step successively, wherein dispersion steps, swelling step and dissolving step time used account for respectively 18～22%, 56～64%, 18～22% of swelling dissolving step total time, the temperature of dispersion steps is controlled at 0 ℃～25 ℃, shear rate≤200 second
-1, the temperature of swelling step is controlled at 90 ℃～120 ℃, shear rate 200 seconds
-1～400 seconds
-1, the temperature of swelling step is controlled at 150 ℃～250 ℃, shear rate 400 seconds
-1～900 seconds
-1
The present invention creatively adopts the semicontinuous swelling of kneader dissolving ultra-high molecular weight polyethylene, the swelling course of dissolution to ultra-high molecular weight polyethylene disperse, swelling and dissolving.
The present invention is subjected to shearing force effect fracture for reduce molecular weight of polyethylene as far as possible, or be heated and degrade, temperature one height in dispersion steps, ultra-high molecular weight polyethylene surface swelling can be adhered to one another, cause inhomogeneous, therefore adopt lower temperature in dispersion steps, purpose is that polyethylene particle is dispersed in solvent, does not make its reunion.
In the swelling step, be penetrated between large molecule in order to make the solvent uniformly penetrating immerse polyethylene particle, it is inner that small solvent molecule penetrates into people's macromolecule, strut strand, increase its volume, form the polymer of swelling, this stage needs uniform temperature, time and higher shear rates to peel off the large molecule that the polyethylene particle surface has been permeated, and solvent is carried out to finer and close crystal region from polyethylene loose amorphous region.
Due to nonpolar crystalline state polymers such as polyethylene, in the time of need to being heated near its fusing point, lattice is destroyed, becomes after amorphous state small molecule solvent and just can be diffused into the inner and dissolving gradually of polymer, and therefore dissolving step of the present invention is through two processes, at first be the destruction of crystalline phase, need heat absorption; Then the be destroyed polymer of lattice and mixing of solvent makes the segments all on macromolecular chain can diffusion motion, forms the homogeneous system that molecule disperses, and finally obtains the spinning solution of transparent homogeneous.
The present invention has advantages of fast, the uniform dissolution ultra-high molecular weight polyethylene.It adopts lower processing temperature, shorter process time and effectively prevent the degraded of ultra-high molecular weight polyethylene than low shear rate, thus improved the strength and modulus of polyethylene fiber, the coefficient of dispersion (coefficient of variation of the various mechanical properties of fiber.The CV value) lower.Single screw extrusion machine of the present invention only plays to be extruded and depressurization, does not participate in course of dissolution, has exempted dissolving to the solution requirement of the time of staying in screw rod, and the diameter of screw rod can be fixed by the output requirement, is not subjected to the restriction of draw ratio, improves production capacity and becomes possibility.Kneader of the present invention also has automatic cleaning action, can give continuously the single screw extrusion machine continuous feeding simultaneously, has guaranteed the continuous discharge of single screw extrusion machine, thereby has improved production capacity, has realized the production of scale.
The invention has the beneficial effects as follows that the preparation method is simple, simple to operate, output is high, and output is greater than 300 ton/years.
Properties of product:
(1) intensity 〉=32cn/dtex (general 30);
(2) fiber molecule amount degraded≤35% (general 50%);
(3) enlarged-diameter of the visual screw rod of output 〉=300 ton/year, maximum production capacity≤200 ton/years at present;
(4) the dissolving shear time is in 20min.Greatly reduced macromolecules degradation, degradation rate 15% left and right that can descend.
The specific embodiment
In order to make technological means of the present invention, creation characteristic, to reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
The high production capacity production method of a kind of high-strength high-modulus polyethylene fiber provided by the present invention, comprise swelling dissolving step, filtration step, spray silk step, cryocoagulation step, predraft step, extraction step, drying steps, ultra-drawing step, coiling step, wherein filtration step, a spray silk step, cryocoagulation step, predraft step, extraction step, drying steps, ultra-drawing step, coiling step are identical with the manufacturing technique of existing polyethylene fiber.Repeat no more in this present invention.
Characteristics of the present invention are exactly at the swelling dissolving step, describe the present invention in detail below in conjunction with specific embodiment.Kneader of the present invention is the kneader with the two kneading blades that drive separately by two motors.Carry out speed governing and change shear rate by separately mediating blade to one respectively.
Embodiment 1
Be 12% to inject respectively and carry out the swelling dissolving in kneader the ultra-high molecular weight polyethylene powder of relative average molecular mass 4,500,000 and 70# white oil according to nominal weight concentration, at first be filled with nitrogen, controlling temperature is 24 ℃, and shear rate is 180 seconds
-1, carry out the dispersion of ultra-high molecular weight polyethylene powder, the time is 4 minutes, then temperature is risen to 120 ℃, shear rate rises to 350 seconds
-1, carry out swelling, the time is 12 minutes, and end temperature rises to 250 ℃, and shear rate rises to 900 seconds
-1, to dissolve, the time is 4 minutes, obtains transparent homogeneous spinning solution; Then quantitatively spinning solution is fed in single screw extrusion machine while stirring and extrude, wherein the single screw extrusion machine diameter is 95mm, the inlet temperature of spinning solution feeding single screw extrusion machine is controlled at 120 ℃～200 ℃, middle extrusion temperature is 120 ℃～250 ℃, outlet temperature is 200 ℃～260 ℃, and the single screw extrusion machine rotating speed is 100rpm.The fibre strength that finally obtains reaches 30cN/dtex, and modulus is more than 1000cN/dtex, and annual production can reach 300 tons.
Embodiment 2
Be 10% to inject respectively and carry out the swelling dissolving in kneader the ultra-high molecular weight polyethylene powder of relative average molecular mass 4,220,000 and 70# white oil according to nominal weight concentration, at first be filled with nitrogen, controlling temperature is 22 ℃, and shear rate is 150 seconds
-1, carry out the dispersion of ultra-high molecular weight polyethylene powder, the time is 4 minutes, then temperature is risen to 100 ℃, shear rate rises to 380 seconds
-1, carry out swelling, the time is 12 minutes, and end temperature rises to 240 ℃, and shear rate rises to 800 seconds
-1, to dissolve, the time is 4 minutes, obtains transparent homogeneous spinning solution; Then quantitatively spinning solution is fed in single screw extrusion machine while stirring and extrude, wherein the single screw extrusion machine diameter is 75mm, the inlet temperature of spinning solution feeding single screw extrusion machine is controlled at 120 ℃～200 ℃, middle extrusion temperature is 120 ℃～250 ℃, outlet temperature is 200 ℃～260 ℃, and the single screw extrusion machine rotating speed is 90rpm.The fibre strength that obtains reaches 30cN/dtex, and modulus is more than 1000cN/dtex, and annual production can reach more than 150 tons.
Embodiment 3
Be 8% to inject respectively kneader and carry out the swelling dissolving the ultra-high molecular weight polyethylene powder of relative average molecular mass 4,400,000 and 70# white oil according to nominal weight concentration, at first be filled with nitrogen, controlling temperature is 20 ℃, and shear rate is 150 seconds
-1, carry out the dispersion of ultra-high molecular weight polyethylene powder, the time is 4 minutes, then temperature is risen to 100 ℃, shear rate rises to 300 seconds
-1, carry out swelling, the time is 12 minutes, and end temperature rises to 230 ℃, and shear rate rises to 800 seconds
-1, to dissolve, the time is 4 minutes, obtains transparent homogeneous spinning solution; Then quantitatively spinning solution is fed in single screw extrusion machine while stirring and extrude, wherein the single screw extrusion machine diameter is 85mm, the inlet temperature of spinning solution feeding single screw extrusion machine is controlled at 120 ℃～200 ℃, middle extrusion temperature is 120 ℃～250 ℃, outlet temperature is 200 ℃～260 ℃, and the single screw extrusion machine rotating speed is 150rpm.The fibre strength that finally obtains reaches 30cN/dtex, and modulus is more than 1000cN/dtex, and annual production can reach 300 tons.
Above demonstration and described basic principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and specification just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (1)
1. the production method of a high-strength high-modulus polyethylene fiber, it is characterized in that, be 12% to inject respectively and carry out the swelling dissolving in kneader the ultra-high molecular weight polyethylene powder of relative average molecular mass 4,500,000 and 70# white oil according to nominal weight concentration, at first be filled with nitrogen, controlling temperature is 24 ℃, and shear rate is 180 seconds
-1, carry out the dispersion of ultra-high molecular weight polyethylene powder, the time is 4 minutes, then temperature is risen to 120 ℃, shear rate rises to 350 seconds
-1, carry out swelling, the time is 12 minutes, and end temperature rises to 250 ℃, and shear rate rises to 900 seconds
-1, to dissolve, the time is 4 minutes, obtains transparent homogeneous spinning solution; Then quantitatively spinning solution is fed in single screw extrusion machine while stirring and extrude, wherein the single screw extrusion machine diameter is 95mm, the inlet temperature of spinning solution feeding single screw extrusion machine is controlled at 120 ℃～200 ℃, middle extrusion temperature is 120 ℃～250 ℃, outlet temperature is 200 ℃～260 ℃, and the single screw extrusion machine rotating speed is 100rpm; The fibre strength that finally obtains reaches 30cN/dtex, and modulus is more than 1000cN/dtex.
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| CN105839200A (en) * | 2016-03-18 | 2016-08-10 | 上海化工研究院 | Suspension fluid uniform charging method and device |
| CN109666976B (en) * | 2017-10-16 | 2021-04-06 | 中国石油化工股份有限公司 | Method for improving performance of ultra-high molecular weight polyethylene fiber product |
| CN110158160B (en) * | 2019-06-28 | 2024-02-27 | 上海化工研究院有限公司 | Method for preparing ultra-high molecular weight polyethylene fiber by high-concentration gel spinning |
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