CN1448546A - Method for spinning ultra -high strength ultra-high modules polyethylene fibre - Google Patents
Method for spinning ultra -high strength ultra-high modules polyethylene fibre Download PDFInfo
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Abstract
The spinning process of polyethylene fiber with very high strength and very high modulus includes the following steps: melting and extruding material in screw extruder, spraying molten material with the spinning jet in spinning tank, drafting, winding to obtain semi-finished fiber, high-multiplication drafting and re-winding to obtain finished polyethylene fiber. The screw extruder processes the material via heating to melt and shearing, and the high-multiplication drafting can increase the strength of the fiber.
Description
Technical field
The present invention relates to the manufacturing of polyethylene fiber, more particularly, relate to the spinning method for genuine of a kind of superhigh intensity, ultra high modulus polyethylene fiber
Background technology
Superelevation is strong, the ultra high modulus polyethylene fiber, is the novel tec fiber that occurs the end of the eighties, and it is one of the world today's three big tec fibers (comprising carbon fiber, aramid fiber and high-strength and high-modulus weight polyethylene fiber).Because its high molecular high orientation and degree of crystallinity, the strength ratio general fibre exceeds nearly 10 times, and because of its density is low, specific strength and specific modulus are high, has outstanding impact resistance and anti-cutting toughness; Good low-temperature resistance, the chemical stability of corrosion-resistant and UV resistant etc., based on these excellent comprehensive performances, this fiber can be widely used in security protection, aviation, space flight, electronics, weapons, shipbuilding, building materials, physical culture, numerous areas such as medical treatment, as bulletproof jacket, bulletproof halmet, shellproof boots, ballproof cash truck, shield, the armor facing on tank and naval vessel, the parachute hawser, boats and ships ocean engineering hawser, climbing rope, fishnet, racing boat, sailing boat, bowstring, tennis racket, ski, artificial joint, ligament, safty shield, shock resistance containers etc. also can be done the exhausted electric material of special building reinforcing material and superconducting insulation, communication cable supporting material or the like.
This polyethylene fiber is that the polyethylene with super high molecular weight is that the raw material spinning forms, and it is above that its brute force reaches 17.6CN/dtex.All be to spin at present, have only the U.S., Holland, three developed countries of Japan to have the ability to produce with gel method.
As far back as the end of the fifties, advanced country in the world begins utilizing the flexible chain high-molecular polythene to prepare high-strength high-modulus fibre research, and the effort of process many decades just reaches the existing level of production.Dutch DSM N. V. had applied for the powerful polyethylene gel method of superelevation spining technology patent in 1992.U.S. ALLIED company takes the lead in having bought this patent, and through after the technological transformation, level further improves.Japan TOYOBO then with the powerful polyethylene fiber of DSM N. V. Joint Production superelevation.And the MITSUI company of Japan forms unique technique following closely.
Because the powerful polyethylene fiber of superelevation has excellent specific properties such as ultralight, high-tenacity, high mode, range of application is extremely extensive, and development prospect is quite optimistic.The technology of this fiber of spinning belongs to the new and high technology of macromolecular material aspect at present, and developed country monopolizes by only a few, even product does not export to China yet.Therefore, the powerful polyethylene fiber research topic of superelevation is put into the state natural sciences fund problem.
Ultra-high molecular weight polyethylene (is called for short: UHMWPE), be the very excellent thermoplastic engineering plastic of a kind of combination property.At application number be: in " ultra-high molecular weight polyethylene three-component blend and preparation method thereof " patent of invention of 01130158.9 detailed introduction is arranged, because of its have superpower ABRASION RESISTANCE (be iron and steel 8-9 doubly, 4 times of nylon, 27 times of brass); Excellent in impact resistance (being 2 times of Merlon, 5 times of ABS, 15 times of polyformaldehyde), especially rare is still keeps its excellent impact strength in liquid nitrogen-196 ℃; Good drug resistance and corrosion resistance can compare favourably with polytetrafluoroethylene (PTFE), in certain temperature and concentration range, and anti-various corrosive liquids and organic solvent; Coefficient of friction low (its coefficient of kinetic friction is 0.1-0.22) is desirable self-lubricating material; Advantages such as fabulous noise reduction and avirulence, thereby worldwide extremely people's favor, its range of application is very extensive.
But because the melting viscosity high (reaching 109Pa.S) of UHMWPE, the mobile performance extreme difference---its melt index of melting body is almost nil.So, be difficult to directly to melt extrude the spray silk, this be because:
1, because the viscosity of UHMWPE is high, does not become viscous state, but be in high viscoelastic attitude.So add man-hour on the conventional screw extruder, material is difficult to advance along screw rod, rotates together but encase screw rod, is absorbed in the state that can not extrude, forms " material plug ";
2, the coefficient of friction of UHMWPE is extremely low, and powder is very easily skidded in fill process, is difficult for charging;
3, the critical shear rate of UHMWPE is very low, and about 10-2/S can cause when extrusion molding and melt body and break;
4, forming temperature narrow range, very easily oxidative degradation.
Because there is above-mentioned difficult point in the processing of UHMWPE, so, the technology and the equipment of the freezing gel method spinning fibre behind the solvent dilution all adopted both at home and abroad at present.But be to use the equipment of gel method spinning Technology Need various, cost is high, and complex process, easily causes environmental pollution.
Summary of the invention
The technical problem to be solved in the present invention is, above-mentioned defective at the gel method spining technology that has polyethylene fiber now, a kind of new polyethylene fiber spinning method for genuine is provided, can utilize less equipment, more simple technical flow spins polyethylene fiber, reduce cost, reduce environmental pollution simultaneously.
The present invention can be achieved through the following technical solutions, and the spinning method for genuine of a kind of superhigh intensity, ultra high modulus polyethylene fiber is characterized in that, may further comprise the steps:
A, ready super-high molecular weight polythene blending raw material is sent into screw rod melt extruded machine, carry out melt process, and send by its rotary screw;
B, the raw material of molten condition is sent into manifold by its spinning head spray silk, obtain the semi-finished product silk through giving reeling after drawing-off is handled again;
C, described semi-finished product silk is carried out the multiple tracks high drafting handle;
Obtain finished product polyethylene fiber silk behind d, the coiling.
According to method of the present invention, in described step a, raw material quantitatively is sent in the described screw rod melt extruded machine with mixing charger.
According to method of the present invention, in described step a, described screw rod melt extruded machine carries out melt process by the shearing force that heating and the rotation of its screw rod are produced to raw material.Be provided with three temperature sections in the described screw rod melt extruded machine: the temperature of input section is 220-240 ℃, and second section temperature is 260-300 ℃, and the 3rd section temperature is 280-320 ℃; The temperature of the output head of described screw rod melt extruded machine is 280-300 ℃.
According to method of the present invention, in described step b, it is constant that described manifold temperature inside keeps, and the measuring pump metering of the raw material of molten condition in manifold, delivers to spinning head through melt pipe again and spray silk.Wherein provide heat to keep described manifold temperature inside constant by diphenyl boiler.
According to method of the present invention, in described step b, comprise that also the silk to being sprayed carries out the step of quenching processing and oiling treatment, deliver to by the path then and give drafting system and give drawing-off and handle, reel and obtain the semi-finished product silk by preceding spinning up-coiler then.Wherein, adopt industrial air-conditioning to carry out quenching and handle, so that the silk of ejection keeps unformed state or alap degree of crystallinity; Adopt the silk oiling device to carry out oiling treatment, to increase a mutual affinity that is sprayed and to eliminate static.
According to method of the present invention, multiple tracks high drafting among the described step c is handled and specifically be may further comprise the steps: after described semi-finished product silk is sent into first heater and heated, drawn by first drafting system, to increase the intensity of silk; Repeat described heating and drafting step, up to described semi-finished product filament drafting more than 70 times; By the annealing device heat treatment of finalizing the design, make strand that enough relaxation abilities be arranged and eliminate internal stress; Behind thermal conductance roll dies and godet roller, deliver to the finished silk coiler device and reel.
According to method of the present invention, between described step a and step b, also comprise with the raw material of filter and filtering to remove the step of impurity to described molten condition.
The invention provides a kind of new polyethylene fiber spinning method for genuine, technological process is simple, can satisfy industrial production requirement, but and energy savings, reduce to pollute, the protection environment.
The invention will be further described below in conjunction with drawings and Examples.
Description of drawings
Fig. 1 is the simple and easy flow chart of polyethylene fiber spinning method for genuine of the present invention;
Fig. 2 is the flow chart of fore-spinning in the polyethylene fiber spinning method for genuine of the present invention;
Fig. 3 is the schematic diagram of the preceding spinning equipment corresponding with flow chart shown in Fig. 2;
Fig. 4 is the schematic diagram of multiple tracks high drafting process in the polyethylene fiber spinning method for genuine among the present invention.
The specific embodiment
Basic step of the present invention wherein to melt the extraordinary ultra-high molecular weight polyethylene of liquid flowability as raw material, is made the blend PP Pipe Compound as shown in Figure 1, utilizes that fusion method spinning superelevation is strong, the polyethylene fiber of ultra high modulus, forms new technological break-through.As can be seen from Figure 1, spin before method of the present invention comprises and the multiple tracks high drafting handled for two steps greatly.In fore-spinning, at first ready raw material is sent into screw rod melt extruded machine, carry out melt process, and send by its rotary screw; Then the raw material of molten condition is sent into manifold by its spinning head spray silk, reeled after drawing-off is handled through giving again, obtain the semi-finished product silk.In multiple tracks high drafting treatment process, described semi-finished product silk is carried out the multiple tracks high drafting handle; Reel then and obtain finished product polyethylene fiber silk.
In a preferred embodiment of the invention, the flow process of fore-spinning and corresponding preceding spinning equipment are distinguished as shown in Figures 2 and 3, and fore-spinning specifically may further comprise the steps:
1, ready raw material quantitatively is sent to screw rod melt extruded machine 2 through mixing charger 1, wherein adopts the forced action type quantifying feed.
2, screw rod melt extruded machine carries out melt process by the shearing force that heating and the rotation of its screw rod produce to raw material; For making the abundant fusion plastification of raw material, be provided with three temperature sections in the screw rod melt extruded machine 2: the temperature of input section is 220-240 ℃, and second section temperature is 260-300 ℃, and the 3rd section temperature is 280-320 ℃; The temperature of the output head of screw rod melt extruded machine is 280-300 ℃.
3, the raw material with 3 pairs of molten conditions of filter filters, and to remove impurity wherein, sends into manifold 4 then.
4, as can be seen from Figure 2, manifold inside is provided with measuring pump, melt pipe and spinning head successively, and provides heat so that the manifold temperature inside keeps constant by diphenyl boiler.The raw material of molten condition through measuring pump metering, deliver to spinning head through melt pipe again and spray silk.For keeping temperature even, the output head of screw rod melt extruded machine 2 all can be put into manifold to this section of manifold spinning head, the heating carrier that is provided by diphenyl boiler keeps temperature constant.
5, the silk that utilizes 5 pairs of chilling apparatus to be sprayed carries out the quenching processing, makes the silk of ejection keep unformed state or hang down as far as possible that degree of crystallinity is arranged, and wherein adopts the industrial air-conditioning unit that cold is provided.The raw material of molten condition carries out quenching immediately behind spinning head spray silk, can make the silk of ejection keep unformed degree of crystallinity that maybe may be low like this, is beneficial to improve the uniformity of level of stretch and stretching.In addition, under lower temperature, crystallization nucleation speed is fast, and the nucleus number that is generated in the unit volume is many, and spherocrystal is less, forms stable thin neck easily in stretching, thereby obtains the better physical mechanical performance.
6, adopt the silk oiling device to carry out oiling treatment, to increase a mutual affinity that is sprayed and to eliminate static.
7, with the silk after handling give by spinning shaft 6 and spin up-coiler 7 before sending into after the drawing-off and reel and obtain the semi-finished product silk.
Multiple tracks high drafting treatment process of the present invention only carries out the fiber of high drafting being higher than vitrification point, being lower than between the melting temperature and carrying out, and just has high strength.Be to be the special-purpose drawing machine of the present invention's configuration as shown in Figure 4, it is to satisfy superhigh intensity, the requirement of ultra high modulus fibre technology, realizes the key equipment of suitability for industrialized production.Can make the macromolecular chain of material reach Gao Juxiang degree and high-crystallinity by this equipment, to realize the high-strength characteristic of fiber.As can be seen from Figure 4 its concrete steps.
At first raw material thread 1 is sent into first heater 3 by feeding unit 2 and heat, send into first drafting system 4 again and draw.
Send into second heater 5 then and carry out heat treated, send into second drafting system 6 again and draw.Raw material thread is after twice heating and drawing-off processing, the molecule segment warm-up movement increases, accelerated relaxation, silk is under tension, produce thin neck, and be arranged in many little shape filament crystals along draw direction, the fiber that is made of thread crystallite bundle in the thin neck is arranged along draw direction, and strand is orientated along draw direction.Through multiple tracks stretching back (draw ratio is not less than 70 times), the intensity of silk can reach the highest.
Then by annealing device 7 heat treatment of finalizing the design, make strand that enough relaxation abilities be arranged and eliminate internal stress; Because monofilament is in stretching, its molecule segment may produce and relatively move and crystallization again, is easy to generate internal stress, after external force is cancelled, can relax gradually and produce and shrink, for eliminating this phenomenon, need heat-treat, make strand that enough relaxation abilities be arranged, reach the purpose of eliminating internal stress.
At last, deliver to finished silk coiler device 10 and reel, obtain the polyethylene fiber silk of finished product through thermal conductance roll dies 8, godet roller 9.
By above technology, can obtain the spinning fiber number is 330-1650/dtex, and intensity is 17.6CN/dtex, and modulus is the superelevation brute force of 882.3CN/dtex, the polyethylene fiber of ultra high modulus.
The melt spinning method production technology of the present invention's initiative adopts ultra-high molecular weight polyethylene as batch mixing, produces with spinning of screw rod melt extruded and multiple tracks high drafting method, facility compact, production procedure is short, and technology is simple, cost is low, and is pollution-free, meets the national environmental protection policy.The ultra high molecular weight polyethylene alloy fiber of this explained hereafter has following characteristics: intensity height, silk tensile break strength height; Shock resistance, the powerful height of anti tear; Proportion is little, in light weight; Fabric has effective opposing puncture and anti-tear breach extended capability; Anti scuffing; The UV resistant irradiation; Corrosion-resistant; Hydrophobic material can (comprise seawater) and keep stable in water; Electrical insulating property is good.
Claims (10)
1, the spinning method for genuine of a kind of superhigh intensity, ultra high modulus polyethylene fiber is characterized in that, may further comprise the steps:
A, ready super-high molecular weight polythene blending raw material is sent into screw rod melt extruded machine, carry out melt process, and send by its rotary screw;
B, the raw material of molten condition is sent into manifold by its spinning head spray silk, obtain the semi-finished product silk through giving reeling after drawing-off is handled again;
C, described semi-finished product silk is carried out the multiple tracks high drafting handle;
Obtain finished product polyethylene fiber silk behind d, the coiling.
2, method according to claim 1 is characterized in that, in described step a, with mixing charger raw material quantitatively is sent in the described screw rod melt extruded machine.
3, method according to claim 1 is characterized in that, in described step a, described screw rod melt extruded machine carries out melt process by the shearing force that heating and the rotation of its screw rod are produced to raw material.
4, method according to claim 3 is characterized in that, is provided with three temperature sections in the described screw rod melt extruded machine: the temperature of input section is 220-240 ℃, and second section temperature is 260-300 ℃, and the 3rd section temperature is 280-320 ℃; The temperature of the output head of described screw rod melt extruded machine is 280-300 ℃.
5, method according to claim 1 is characterized in that, in described step b, it is constant that described manifold temperature inside keeps, and the measuring pump metering of the raw material of molten condition in manifold, delivers to spinning head through melt pipe again and sprays silk.
6, method according to claim 5 is characterized in that, provides heat to keep described manifold temperature inside constant by diphenyl boiler.
7, method according to claim 1, it is characterized in that, in described step b, also comprise the step of the silk that is sprayed being carried out quenching processing and oiling treatment, deliver to by the path then and give drafting system and give drawing-off and handle, reel and obtain the semi-finished product silk by preceding spinning up-coiler then.
8, method according to claim 7 is characterized in that, adopts industrial air-conditioning to carry out quenching and handles, so that the silk of ejection keeps unformed state or alap degree of crystallinity; Adopt the silk oiling device to carry out oiling treatment, to increase a mutual affinity that is sprayed and to eliminate static.
9, method according to claim 1 is characterized in that, the multiple tracks high drafting among the described step c is handled and specifically be may further comprise the steps:
After described semi-finished product silk sent into first heater and heat, draw by first drafting system, to increase the intensity of silk;
Repeat described heating and drafting step, up to described semi-finished product filament drafting more than 70 times;
By the annealing device heat treatment of finalizing the design, make strand that enough relaxation abilities be arranged and eliminate internal stress;
Behind thermal conductance roll dies and godet roller, deliver to the finished silk coiler device and reel.
10, according to the described method in arbitrary top among the claim 1-9, it is characterized in that, between described step a and step b, also comprise with the raw material of filter and filtering to remove the step of impurity to described molten condition.
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| CN100427653C (en) * | 2006-11-24 | 2008-10-22 | 东华大学 | Prepn and application of jelly fiber of polyethylene in ultrahigh molecular weight |
| WO2009105926A1 (en) * | 2008-02-26 | 2009-09-03 | 山东爱地高分子材料有限公司 | 10-50 g/d high strength polyethylene fiber and preparation method thereof |
| CN101935894A (en) * | 2010-09-02 | 2011-01-05 | 王庆昭 | Method and equipment for preparing ultrahigh molecular weight polyethylene fibers |
| CN101629331B (en) * | 2008-07-17 | 2011-01-26 | 宁波荣溢化纤科技有限公司 | Method for drawing ultra-high molecular weight polyethylene fiber |
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