CN101476170A - Method and apparatus for producing high strength, high modulus polyethylene filament by melt drawing - Google Patents
Method and apparatus for producing high strength, high modulus polyethylene filament by melt drawing Download PDFInfo
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- CN101476170A CN101476170A CNA200810241731XA CN200810241731A CN101476170A CN 101476170 A CN101476170 A CN 101476170A CN A200810241731X A CNA200810241731X A CN A200810241731XA CN 200810241731 A CN200810241731 A CN 200810241731A CN 101476170 A CN101476170 A CN 101476170A
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Abstract
The invention discloses a method for producing polythene fiber with high strength and high modulus by melting fiber drawing and a device thereof. The method includes steps as follows: blend composition of polythene with super high molecular weight and three element blend composition of polythene with super high molecular weight are used as raw material, the raw material is spout fibre adobe after melted through a screw extruder, the fibre adobe is preset drafted after cooling, then low power drafted after once heating, then high power drafted after twice heating, finally is processed heat processing for obtaining polythene fiber with high strength and high modulus. The screw extruder, a cooling mechanism, a drafting machine processing preset drafting, an once heating mechanism, a low power drafting machine, a twice heating mechanism, a high power drafting machine, a heat processing mechanism, a winding reeling machine are arranged in the device orderly. The invention provides a producing method with simple technique, short producing flow, low cost and no pollution aiming at problem that UHMWPE melting spout fibre process has difficult to spin, and provides a device with compact equipment and easy to operate.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to the method for a kind of melt drawing production high strength, high modulus polyethylene filament.The polyethylene filament that this method is produced can be widely used in numerous areas such as mining industry, building materials, rope, as hawser, boats and ships ocean engineering hawser, climbing rope, fishnet, racing boat, sailing boat, bowstring, ski, mine safety protection network, various screen cloth, enhancing shock resistance container etc., also can do the building trade reinforcing material, and replace glass fibre or the like.
Background technology
Ultra-high molecular weight polyethylene (is called for short: UHMWPE), it is the very excellent thermoplastic engineering plastic of a kind of combination property, its production process is similar to high density polyethylene (HDPE) with molecular shape, all be to adopt Ziegler catalyst to form branching linear molecule chain seldom through coordination polymerization, its difference is the length of strand, i.e. the size of molecular weight.The molecular weight of common high density polyethylene (HDPE) is generally several ten thousand to hundreds of thousands, and the molecular weight of synthetic ultra-high molecular weight polyethylene surpasses 1,500,000 under certain condition, even reaches 10,000,000.Strand just because of ultra-high molecular weight polyethylene is long especially, so it is good especially to have physical mechanical and chemical property, the especially ABRASION RESISTANCE of many uniquenesses, ranks first in known plastic.
High molecular weight has been given it and has been had common polythene and other engineering plastics unrivaled special performances: 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, (reach 10 because the melting viscosity of UHMWPE is high
9Pa.S), mobile performance extreme difference (its melt index of melting body is almost nil).So, be difficult to directly melt extrude the spray silk, because there is great difficulty in the processing of UHMWPE, so, domestic and international technology and the equipment that also UHMWPE is not processed into silk at present.
Summary of the invention
The technical problem to be solved in the present invention is, there is difficulty in melt-out spinning processing at UHMWPE, can't become the problem of silk, provide that a kind of technology is simple, production procedure is short, cost is low, the method for free of contamination melt drawing production high strength, high modulus polyethylene filament.
The technical problem that the present invention further will solve is, the device of a kind of facility compact, easy-operating melt drawing production high strength, high modulus polyethylene filament is provided.
The technical solution adopted for the present invention to solve the technical problems is: the method for a kind of melt drawing production high strength, high modulus polyethylene filament, selecting for use and making the three-component blend that the ultra-high molecular weight polyethylene blend of modifier or ultra-high molecular weight polyethylene, organosilicon, liquid crystal polymer form with organosilicon is raw material, described raw material is sprayed into a base after the screw extruder fusion, silk base cooling back preliminary draft, once heating the back low power then stretches, carry out super drawing after the post bake again, obtain high strength, high modulus polyethylene filament after heat-treating at last.
The method of melt drawing production high strength, high modulus polyethylene filament preferably includes following steps:
A, raw material is joined screw extruder, raw material is subjected to temperature and shearing force in barrel effect is melted, and filters out impurity, becomes a base by spinning head spray silk again;
B, silk base keep amorphous state or low-crystallinity through the cooling body quenching;
C, cooled silk base carry out the low speed preliminary draft by drawing machine, and the draft speed of described preliminary draft is the extruded velocity that is higher than screw extruder;
Behind D, the preliminary draft, the silk base enters water tank and carries out water-bath heating;
After E, the heating, the silk base carries out low power by drawing machine and stretches, and silk produces thin neck under tension;
After F, low power stretch, carry out post bake again, heating-up temperature is higher than 100 ℃, and the molecule segment warm-up movement of silk increases, and has accelerated relaxation;
After G, the heating, the silk base carries out super drawing by drawing machine, and strand is orientated along draw direction;
After H, the super drawing, bigger through the powerful silk shrinkage factor that stretches of high power, the internal stress of monofilament is also bigger, therefore, needs through heat treatment mechanism high-temperature heat treatment, to reduce the shrinkage factor and the internal stress of monofilament, could form the silk of high strength, high-modulus at last.
In order to make the abundant fusion plastification of raw material, described each section of screw extruder temperature is preferred: one section 220~240 ℃; Two sections 260~300 ℃; Three sections 280~300 ℃; 280 ℃ of heads.
Preferred 5~20 ℃ of described silk base chilling temperature can make the quenching of base silk like this, keeps unformed degree of crystallinity that maybe may be low, 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.
Preferred 80~95 ℃ of the temperature of described water-bath heating.
Preferred 105~130 ℃ of the temperature of described post bake.
The speed that described low power stretches is: with the differential surface speed of preliminary draft be 1:10~20;
The speed of described super drawing is: with the differential surface speed of preliminary draft be 1:40~60;
Described heat treated temperature is that heat treated temperature is 90~110 ℃.The degree of crystallinity of monofilament is improved as much as possible, and intensity is improved.
In the device of a kind of melt drawing production high strength, high modulus polyethylene filament, be placed with screw extruder, cooling body successively, carry out the drawing machine of preliminary draft, heating arrangements, low power stretching-machine, post bake mechanism, super drawing machine, annealing device, winding winder.
Screw extruder extrusion place is provided with spinning head, and the screw extruder charging aperture is provided with loading hopper, and described cooling body adopts cooling water tank; A described heating arrangements adopts heating water tank; Described post bake mechanism's employing hot air type or heat-conducting oil heating case; Described annealing device adopts hot-rolling formula annealing device.
The good characteristic that polyethylene filament had that the present invention produces, the reason of high-tenacity, high-modulus is exactly the molecular structure of its linear long-chain.Strand is arranged in order, and wide-spread conformation is simultaneously with density, crystallinity change.Big molecule axial orientation in the silk after owing to be stretched, and the molecular separating force of other types, the strand number that adds tension force that bears of silk has increased, thereby the fracture strength of silk is significantly improved.Simultaneously, the strong energy of forming between the macromolecular atom of covalence key is high, so have the anti-ultraviolet property that is more than other material.
The present invention adopts and to make the three-component blend that the ultra-high molecular weight polyethylene blend of modifier or ultra-high molecular weight polyethylene, organosilicon, liquid crystal polymer form with organosilicon is raw material, produce with spinning of screw rod melt extruded and twice extension, production procedure is short, technology is simple, cost is low, pollution-free, meet the national environmental protection policy.The ultra high molecular weight polyethylene alloy silk of this explained hereafter has following characteristics:
1. intensity height, silk tensile break strength height;
2. shock resistance, the powerful height of anti tear;
3. proportion is little, in light weight;
4. anti scuffing;
5. UV resistant irradiation;
6. corrosion-resistant;
7. hydrophobic material can (comprise seawater) and keep stable in water;
8. electrical insulating property is good.
Present device compactness, easy to operate provides a kind of device that can satisfy the new varieties silk of suitability for industrialized production, energy savings, protection environment.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is a process chart of the present invention;
Fig. 2 is the structural representation of the embodiment of the invention.
The specific embodiment
The three-component blend that the present invention adopts organic-silicon-modified ultra-high molecular weight polyethylene blend or ultra-high molecular weight polyethylene, organosilicon, liquid crystal polymer to form is a raw material.
Ultra-high molecular weight polyethylene blend adopts organosilicon to form blend composition as the Modification of UHMWPE agent, and its component comprises ultra-high molecular weight polyethylene 85~97%, organosilicon 3~15%, antioxidant 0.2~2%.
Ultra-high molecular weight polyethylene three-component blend is formed by following components in weight percentage blend: ultra-high molecular weight polyethylene 88~94%, organosilicon 3~7%, liquid crystal polymer 2~5%, calcium stearate 0.2~2%, antioxidant 0.1~1%.
The antioxidant that adopts is phenolic antioxidant, and phenolic antioxidant is specifically selected antioxidant 1010 or B215 for use.
Be illustrated in figure 1 as process chart, the method for melt drawing production high strength, high modulus polyethylene filament may further comprise the steps:
A, raw material is joined screw extruder, raw material is subjected to temperature and shearing force in barrel effect is melted, and filters out impurity by filter, becomes a base by spinning head spray silk again; In order to make the abundant fusion plastification of raw material, described each section of screw extruder temperature is: one section 220~240 ℃; Two sections 260~300 ℃; Three sections 280~300 ℃; 280 ℃ of heads.
B, silk base are through water tank water-bath quenching, and the temperature of described silk base cooling water tank can be selected 5 ℃, 10 ℃, 15 ℃, 20 ℃, and such temperature silk can keep amorphous state or low-crystallinity;
C, cooled silk base carry out the low speed preliminary draft by drawing machine, and the draft speed of described preliminary draft is the extruded velocity that is higher than screw extruder;
Behind D, the preliminary draft, the silk base enters water tank and carries out water-bath heating; The temperature of a water-bath water tank can be selected 80 ℃, 85 ℃, 90 ℃, 95 ℃.
After E, the heating, the silk base carries out low power by drawing machine and stretches, and the speed that described low power stretches is: can select 1:10,1:15,1:20 with the differential surface speed of preliminary draft, silk produces thin neck under tension;
After F, low power stretch, carry out post bake again, the temperature of described post bake can be selected 105 ℃, 110 ℃, 120 ℃, 130 ℃, and heating increases the molecule segment warm-up movement of silk, has accelerated relaxation;
After G, the heating, the silk base carries out super drawing by drawing machine, and the speed of described super drawing is: select 1:40,1:50,1:60 with the differential surface speed of preliminary draft, stretching can make strand be orientated along draw direction;
After H, the super drawing, bigger through the powerful silk shrinkage factor that stretches of high power, the internal stress of monofilament is also bigger, therefore, need, to reduce the shrinkage factor and the internal stress of monofilament through heat treatment mechanism high-temperature heat treatment, the last silk that could form high strength, high-modulus, described heat treated temperature is 90~110 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃ of available selections, wherein preferred 100 ℃.
As shown in Figure 2, the device of a kind of melt drawing production high strength, high modulus polyethylene filament is placed with screw extruder 2, cooling water tank 2 successively, carries out the multiple roll drawing machine 4 of preliminary draft, once heats heating water tank 6, low power stretching-machine 7, hot air type or heat conducting oil type heating cabinet 8, super drawing machine 9, annealing device 10, twines winder 11.Charging aperture at screw extruder 2 is provided with loading hopper 1, and described low power stretching-machine 7, super drawing machine 9 all are the multiple roll stretching-machine.Described annealing device adopts hot-rolling formula annealing device.
Claims (10)
1, the method for a kind of melt drawing production high strength, high modulus polyethylene filament, selecting for use and making the three-component blend that the ultra-high molecular weight polyethylene blend of modifier or ultra-high molecular weight polyethylene, organosilicon, liquid crystal polymer form with organosilicon is raw material, it is characterized in that, described raw material is sprayed into a base after the screw extruder fusion, silk base cooling back preliminary draft, once heating the back low power then stretches, carry out super drawing after the post bake again, heat-treat at last and obtain high strength, high modulus polyethylene filament.
2, the method for melt drawing production high strength according to claim 1, high modulus polyethylene filament is characterized in that, may further comprise the steps:
A, extrude after raw material joined the screw extruder fusion, become a base by spinning head spray silk more after filtration;
B, silk base keep amorphous state or low-crystallinity through the cooling body quenching;
C, cooled silk base carry out the low speed preliminary draft by drawing machine, and the draft speed of described preliminary draft is the extruded velocity that is higher than screw extruder;
Behind D, the preliminary draft, the silk base enters water tank and carries out water-bath heating;
After E, the heating, the silk base carries out low power by drawing machine and stretches;
After F, low power stretch, carry out post bake again, heating-up temperature is higher than 100 ℃;
After G, the heating, the silk base carries out super drawing by drawing machine;
After H, the super drawing, form finished product through heat treatment mechanism high-temperature heat treatment.
3, the method for melt drawing production high strength according to claim 1 and 2, high modulus polyethylene filament is characterized in that, described each section of screw extruder temperature is: one section 220~240 ℃; Two sections 260~300 ℃; Three sections 280~300 ℃; 280 ℃ of heads.
4, the method for melt drawing production high strength according to claim 1 and 2, high modulus polyethylene filament is characterized in that, described silk base chilling temperature is 5~20 ℃.
5, the method for melt drawing production high strength according to claim 2, high modulus polyethylene filament is characterized in that, the temperature of described water-bath heating is 80~95 ℃; The temperature of described post bake is 105~130 ℃.
6, the method for melt drawing production high strength according to claim 1 and 2, high modulus polyethylene filament is characterized in that, the speed that described low power stretches is: with the differential surface speed of preliminary draft be 1:10~20.
7, the method for melt drawing production high strength according to claim 2, high modulus polyethylene filament is characterized in that the speed of described super drawing is: with the differential surface speed of preliminary draft be 1:40~60.
8, the method for melt drawing production high strength according to claim 1 and 2, high modulus polyethylene filament is characterized in that, heat treated temperature is 90~110 ℃.
9, the device of a kind of melt drawing production high strength, high modulus polyethylene filament, it is characterized in that, be placed with screw extruder, cooling body successively, carry out the drawing machine of preliminary draft, heating arrangements, low power stretching-machine, post bake mechanism, super drawing machine, annealing device, winding winder.
10, the device of melt drawing production high strength according to claim 9, high modulus polyethylene filament is characterized in that, screw extruder extrusion place is provided with spinning head, and the screw extruder charging aperture is provided with loading hopper, and described cooling body adopts cooling water tank; A described heating arrangements adopts heating water tank; Described post bake mechanism's employing hot air type or heat conducting oil type heating cabinet; Described annealing device is a hot-rolling formula annealing device.
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