CN104818541A - Crosslinked ultrahigh molecular weight polyethylene fiber and wet preparation method thereof - Google Patents
Crosslinked ultrahigh molecular weight polyethylene fiber and wet preparation method thereof Download PDFInfo
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Abstract
The invention relates to a crosslinked ultrahigh molecular weight polyethylene fiber and a wet preparation method thereof. The decreasing rate of the weight-average molecular weight of ultrahigh molecular weight polyethylene caused by radiation or irradiation splitting is less than 10%. The ultrahigh molecular weight polyethylene fiber disclosed by the invention has excellent heat resistance and creep resistance and high mechanical strength, and therefore, the ultrahigh molecular weight polyethylene fiber is especially suitable for preparing bulletproof vests, helmets, lightweight armors, sails, mooring ropes, fishing nets, optical cable reinforcement bodies, parachutes, filter materials, radomes, wind turbine blades and the like which are ultrahigh in mechanical strength and heat resistance.
Description
Technical field
The present invention relates to polyethylene fiber and preparation method thereof, particularly relate to superhigh molecular weight polyethylene fibers and preparation method thereof.
Background technology
Superhigh molecular weight polyethylene fibers is the third generation high-performance fiber occurred after carbon fiber and aramid fiber, there is the mechanical property that other high-performance fiber is incomparable, in addition it also has excellent chemical resistance, weather resisteant, high-energy absorption, shock-resistant, low temperature resistant, wear-resisting, resist bending, anti-cutting, electric insulation, can pass through electron beam or gamma-rays, the multiple excellent properties such as water proofing property, be widely used in military shellproof, security protection, space flight navigation engineering and high-performance, the field such as light composite material and sports apparatus, such as, for such as rope, fishing net, medicine equipment, fabric, lamination, composite product and ballistic protective clothing, anti-cutting fabric, hawser etc.
But, because ultra-high molecular weight polyethylene molecule is only made up of methylene itself, so intermolecular nonpolarity active force, this fiber surface is chemical inertness, add highly crystalline, height-oriented smooth surface that this fiber is formed through super drawing, cause superhigh molecular weight polyethylene fibers itself also to there is many weak points, as fiber poor heat resistance (the highest 70 DEG C), limit the serviceability temperature of fiber.Use the system of superhigh molecular weight polyethylene fibers, especially those ultimate failure patterns being placed in the system under load for a long time cause due to creep, and especially when improving temperature, problem is more serious.Therefore, such system, be particularly intended to that long-term or super-long-term uses those, enough maintenances must be designed and for many years, such as, more than 10 years, and exceed even 30 years in some cases.Owing to easily producing creep, limit the use of this fiber in relevant speciality Application Areas.
Improve the surface adhesiveness energy of superhigh molecular weight polyethylene fibers, surface modification can be carried out to fiber by methods such as chemical reagent etch, Cement Composite Treated by Plasma modification, Corona discharge Treatment, photooxidation surface modification treatment, radiation grafting process, fiber inactive surfaces layer is activated, introduce carboxyl, carbonyl, hydroxyl isopolarity group at nonpolar fiber surface, but these class methods can not improve heat resistance and the creep-resistant property of this fibrid.By using energy-rich radiation irradiation in the presence of a crosslinking agent, cross-linked structure can be introduced superhigh molecular weight polyethylene fibers, thus play the effect of fixing macromolecular chain, heat resistance and the creep resistance of this fibrid can be improved so to a certain extent.But energy-rich radiation irradiation can make ultra-high molecular weight polyethylene macromolecular chain that a large amount of fracture, disproportionation and dehydrogenation occur, thus makes the performances such as the mechanical strength of superhigh molecular weight polyethylene fibers, percentage elongation, resistance to elevated temperatures, creep resistant greatly reduce.
Therefore, a kind of heat resistance to existing excellence of active demand and creep resistance have again superhigh molecular weight polyethylene fibers and the goods thereof of high mechanical properties in the art.
Summary of the invention
One aspect of the present invention is to provide a kind of crosslinked superhigh molecular weight polyethylene fibers, and the weight average molecular weight rate of descent of the ultra-high molecular weight polyethylene caused due to radiation cleavage is less than 10%.
Another aspect of the present invention is to provide the preparation method of above-mentioned superhigh molecular weight polyethylene fibers, and it comprises the steps:
1) ultra-high molecular weight polyethylene spinning solution is provided;
2) spray silk by described spinning solution and form hygrometric state gel precursor;
3) use extractant to extract described hygrometric state gel precursor, form extraction silk;
4) the extraction silk described in drying, removing extractant, obtains dry state gel precursor;
5) allow dry state gel precursor by one or more bath, make dry state gel precursor absorption cross-linking system body lotion wherein, described body lotion contains allyl crosslinking agent and free radical scavenger;
6) at 90-180 DEG C, preferably at the temperature of 120-150 DEG C, the dry state gel precursor absorbing body lotion is drawn one or more additional times; With
7) the dry state gel precursor after stretching is cross-linked, preferably drawing-off or tension force HEAT SETTING again after cross-linking.
Accompanying drawing explanation
Fig. 1 is the general technology flow chart that the present invention prepares superhigh molecular weight polyethylene fibers method.
Fig. 2 is the infared spectrum of conventional superhigh molecular weight polyethylene fibers.
Fig. 3 is the infared spectrum of the superhigh molecular weight polyethylene fibers of one embodiment of the present invention.
Detailed description of the invention
In one preferred embodiment, the initial weight average molecular weight of ultra-high molecular weight polyethylene used during ultra-high molecular weight polyethylene spinning solution for the preparation of the inventive method is 80-1000 ten thousand, is preferably 250-700.
For the preparation of spinning solution is generally low voc solvent, such as include but not limited to benzene,toluene,xylene, cyclohexane, carbon tetrachloride, phenol, trichloro-ethylene, N, N mono-dimethylaniline, tetrahydrochysene bark mutter, 1,1,1 one trichloroethanes, cyclohexanol, n-hexane, n-butanol, cyclohexanone, isopropyl alcohol, normal heptane, N, N dimethyl formamide, N, N mono-dimethylacetylamide, N monomethyl formamide, white oil, paraffin, kerosene, mineral oil, vegetable oil, animal oil, tetrahydronaphthalene, decahydronaphthalenes or their mixture.Preferred low voc solvent includes but not limited to white oil, mineral oil or their mixture.The consumption of low voc solvent, ultrahigh molecular weight polyethylene can be become suitable spinning solution be advisable, is generally 55-97wt%, is preferably 80-97wt%, with the weight of ultra-high molecular weight polyethylene used for benchmark.
In one preferred embodiment, the ultra-high molecular weight polyethylene spinning solution for the preparation of the inventive method also can contain conventional additive, as polarity modifier, antioxidant or their mixture.In spinning solution, the consumption of above-mentioned additive is generally advisable to reach required effect, but should not exceed the consumption of the spinning properties affecting spinning solution.
The object adding polarity modifier is the compatibility in order to improve superhigh molecular weight polyethylene fibers and other resin.Polarity modifier is generally have the unsaturated double-bond that can carry out with fiber reacting in radiation environment and have with the polar group of other resin compatibles as the monomer of ester bond, ehter bond, hydroxyl, phenyl ring etc. or high polymer.The example of polarity modifier includes but not limited to 2-phenoxyethyl acrylate, isodecyl acrylate, laurate acrylate, iso-bornyl acrylate, ring trimethylolpropane acetal acrylate, maleic anhydride, oxolane acrylate or their mixture.Preferred polarity modifier includes but not limited to 2-phenoxyethyl acrylate.
The consumption of above-mentioned polarity modifier is generally 0-10wt%, 0.05-5 % by weight, is preferably 0.05-3wt%, with the weight of ultra-high molecular weight polyethylene for benchmark.
The object adding fiber antioxidant be in order to prevent or suppress superhigh molecular weight polyethylene fibers in processing or use procedure aging.The example of above-mentioned fiber antioxidant includes but not limited to 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 4,4 '-thiobis (6-tertiary butyl-3-methylphenol), four [methylene-3-(3', 5 '-di-tert-butyl-4 '-antelope base phenyl) propionic acid] pentaerythritol ester and triphenyl phosphite, tricresyl phosphite (2,4-di-tert-butyl phenyl) ester, the different monooctyl ester of tricresyl phosphite or tricresyl phosphate benzene methyl or dilauryl thiodipropionate, thio-2 acid bay octadecyl ester, thio-2 acid two (13) ester or their mixture.Preferred fiber antioxidant includes but not limited to 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenols, 4,4 '-thiobis (6-tertiary butyl-3-methylphenol), tricresyl phosphite (2,4-di-tert-butyl phenyl) ester or their mixture.The consumption of above-mentioned fiber antioxidant is generally 0-10wt%, is preferably 0.05-5wt%, is preferably 0.05-3 % by weight, with the weight of ultra-high molecular weight polyethylene for benchmark.
In one preferred embodiment, above-mentioned ultra-high molecular weight polyethylene, low voc solvent and optional polarity modifier and fiber antioxidant are added in screw extruder stirring of fully mixing under heating and pressurized conditions, to reach the object mixed, thus obtained required spinning solution.Above-mentioned screw extruder such as includes but not limited to single screw extrusion machine or double screw extruder.The operating temperature of above-mentioned screw extruder, generally at 120-280 DEG C, is preferably 150-200 DEG C.The rotating speed of screw extruder, generally at 100-200 rev/min, is preferably 100-150 rev/min.The operating pressure of above-mentioned screw extruder, generally at 3-6MPa, is preferably 4-5MPa.
In one preferred embodiment, the spinning solution formed such as is formed hygrometric state gel precursor (i.e. gel fiber) with manifold and spinnerets spray silk.The temperature general control of above-mentioned manifold and spinnerets, at 130-270 DEG C, is preferably 150-200 DEG C.In a preferred embodiment, tentatively can draw stretch hygrometric state gel precursor, the general 1-10 of draw ratio doubly, is preferably 1-5 doubly.
In one preferred embodiment, use extractant to extract described hygrometric state gel precursor, form extraction silk.Use the main purpose of extractant to be by solvent extractions a large amount of in hygrometric state gel precursor bar, to cement out, thus obtain the high-strength polyethylene fiber that " pure " spend.Extractant General Requirements meets economical and practical, safety and environmental protection, and effect of extracting is good again, and nontoxic, tasteless.The example of extractant includes but not limited to C
1-15alkane, aromatic hydrocarbons, halogenated alkane, alkenyl halide or their mixture, be preferably C
6-10alkane, is more preferably C
8-9alkane.The example of extractant includes but not limited to agent for carbon hydrogen detergent 103 or 104, gasoline, dimethylbenzene, carrene, tetrachloro-ethylene or their mixture.Preferred extractant comprises agent for carbon hydrogen detergent 103, agent for carbon hydrogen detergent 104, gasoline or their mixture.In a preferred embodiment, can one or more extraction step be carried out, such as, comprise 1-5 extraction, drying steps, preferred 2-3 extraction, drying steps.
In one preferred embodiment, the extraction silk described in drying, removing extractant, to obtain dry state gel precursor.Dry temperature is generally 20-120 DEG C, is preferably 30-90 DEG C, and the dry time is generally 1-40 minute, is preferably 10-30 minute.In a preferred embodiment, described drying steps can be divided into multiple step to carry out, such as, be divided into 2 steps to carry out.In the 1st step, generally at 20-50 DEG C, preferably at 30-45 DEG C of dry 5-20 minute, preferred 10-15 minute.But in the 2nd step, generally at 50-100 DEG C, preferably at 70-90 DEG C of dry 5-20 minute, preferred 10-20 minute.
In one preferred embodiment, allow the dry state gel precursor of gained by one or more bath, make dry state gel precursor absorption cross-linking system body lotion wherein, described body lotion contains allyl crosslinking agent and free radical scavenger, preferably containing allyl crosslinking agent, free radical scavenger and polymerization inhibitor.
Above-mentioned allyl crosslinking agent is used to be to make the large intermolecular generation of ultra-high molecular weight polyethylene be cross-linked, the webbed cross-linked structure of shape, thus the temperature tolerance and the creep resistance that improve superhigh molecular weight polyethylene fibers.The crosslinking agent used in the present invention has high-temperature stability, can under 150-300 DEG C of environment not autohemagglutination, there is good heat endurance, volatilize little, mate very much with polyolefinic processing temperature of extruding, there will not be autohemagglutination, precipitation, foamed phenomenon.Preferred allyl crosslinking agent is 1-4 allyl crosslinking agent, is more preferably 2-3 polyenoid propyl group crosslinking agent.The example of above-mentioned allyl crosslinking agent includes but not limited to triallyl isocyanuric acid ester, triallyl cyanurate, trimethylol-propane trimethacrylate, ethoxyquin trimethylolpropane triacrylate, glycerol propoxylate triacrylate, three (2-ethoxy) isocyanuric acid triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, 1, 6-hexanediyl ester, ethoxylated bisphenol A diacrylate, dimethacrylate, propylene glycol diacrylate, polyethyleneglycol diacrylate or their mixture.
The consumption of above-mentioned allyl crosslinking agent is generally as the criterion to form enough cross-linked networks in superhigh molecular weight polyethylene fibers.Its consumption is the 0.01-10wt% of superhigh molecular weight polyethylene fibers weight, is preferably 0.05-5 % by weight.
Above-mentioned free radical scavenger be a class can with chemical reaction process in produce can not the living radical effect that exists of long-time stable formed can the material of the free radical that exists of long-time stable or stable molecule, such as phenols, quinones or amine monomers or polymer.The example of above-mentioned free radical scavenger includes but not limited to 2,2-diphenyl-1-trinitrophenyl-hydrazine, 1,4-benzoquinone, tetramethyl-benzoquinone, 2-methyl-2-nitromethane, phenyl-N-tert-butylnitrone or their mixture.
In the present invention, the consumption of above-mentioned free radical scavenger is generally the 0.05-5 % by weight of superhigh molecular weight polyethylene fibers weight, is preferably 0.05-2wt%.
To be a class when its molecule and chain radical reaction form low activity free radical that non-free radical material maybe can not cause thus make to be polymerized the compound stopped above-mentioned polymerization inhibitor.The example of above-mentioned suppression crosslinking agent includes but not limited to 2,5-di-tert-butyl hydroquinone, 2-TBHQ, MEHQ, methylnaphthohydroquinone, hydroquinones, 2,6-di-t-butyl-4 (dimethyl aminomethyl phenol) or their mixtures.
In the present invention, the consumption of above-mentioned polymerization inhibitor is generally the 0-5 % by weight of superhigh molecular weight polyethylene fibers weight, is preferably 0.5-2wt%.
When using ultra-violet radiation, also need in spinning solution to add radical initiator.Radical initiator is the monomer with light sensitive characteristic or the polymer that a class can produce free radical under radiation condition.In the present invention, the example of radical initiator used includes but not limited to cracking type free radical photo-initiation, hydrogen-abstraction free radical photo-initiation, cationic photoinitiator or their mixture.The example of cracking type free radical photo-initiation includes but not limited to benzoin and derivative, benzil derivatives, Dialkoxy acetophenones, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acylphosphine oxide or their mixture.The example of hydrogen-abstraction free radical photo-initiation includes but not limited to that benzophenone or heterocycle arone compounds are as benzophenone (BP), 4-methyl benzophenone, 2,4,6-tri-methyl benzophenone, tetramethyl Michler's keton (MK), tetraethyl Michler's keton (DEMK), the first and second base Michler's keton (MEMK) or their mixtures.The example of cationic photoinitiator includes but not limited to the luxuriant iron of 6-isopropylbenzene (II) hexafluorophosphate, 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl esters or their mixture.
In the present invention, the consumption of above-mentioned radical initiator is generally the 0-10 % by weight of superhigh molecular weight polyethylene fibers weight, is preferably 0.05-5wt%.
In one preferred embodiment, the cross-linking system body lotion for being absorbed by dry state gel precursor generally forms by allyl crosslinking agent, free radical scavenger and optional polymerization inhibitor and radical initiator are added dissolution with solvents.The example of solvent is generally C
1-15alkane, aromatic hydrocarbons, halogenated alkane, alkenyl halide or their mixture, be preferably C
6-10alkane, is more preferably C
8-9alkane.The example of extractant includes but not limited to agent for carbon hydrogen detergent 103 or 104, gasoline, dimethylbenzene, carrene, tetrachloro-ethylene or their mixture.Preferred extractant comprises agent for carbon hydrogen detergent 103, agent for carbon hydrogen detergent 104, gasoline or their mixture.
In a preferred embodiment, described cross-linking system solution contains 1-30wt% allyl crosslinking agent, 0.01-1wt% free radical scavenger, 0-1wt% polymerization inhibitor and 0-10wt% radical initiator, with the weight of extractant for benchmark.
In one preferred embodiment, dry state gel precursor is 5-30 second at total soak time of body lotion, is preferably 5-20 second.
In one preferred embodiment, at 110-180 DEG C, preferably at the temperature of 120-150 DEG C, the dry state gel precursor after absorption body lotion is drawn one or more additional times.Total draw ratio is generally greater than 20 times, is usually greater than 30 times, is preferably 20-150 doubly.
In one preferred embodiment, radiation irradiation is carried out to the rear superhigh molecular weight polyethylene fibers formed that stretches.This radiation can online or off-line carry out.Online mode can be cross-linked after drawing of fiber completes or after drawing-off certain multiple, such as, batch fiber is at a high speed carried out high speed by cross-linking apparatus by actinobacillus device crosslinked, and then to become cylinder to complete crosslinked in take-up.Off-line is crosslinked can, after fiber completes drawing-off, be realized crosslinked, such as, one-tenth cylinder fiber is placed on a kind of rotatable equipment, makes into a fiber and be cross-linked by irradiation apparatus.
Radiation used in the present invention includes but not limited to that ultraviolet radiation, electron beam irradiation, gamma Rays, χ ray are cross-linked, infrared radiation, heat radiation or their combination, be preferably ultraviolet radiation, electron beam irradiation, gamma Rays or their combination.Dosage of radiation used in the present invention is generally 0.01-35Mrad, is preferably 5-18Mrad, is more preferably 5-15Mrad.More particularly, electron beam irradiation dosage is 1-15Mrad, and the ultraviolet irradiation time is 5-20s, gamma-ray irradiation dosage 5-15Mrad; Infrared-ray exposure time 5-20s.
In a particularly preferred embodiment, crosslinked ultra-high-molecular-weight polyethylene fiber of the present invention has the low design feature of the degree of cross linking degree of cross linking that is high and core of peripheral part on its cross section.Above-mentioned crosslinked crosslinking with radiation preferably under allyl crosslinking agent exists.
The present inventor is surprisingly found out that, the superhigh molecular weight polyethylene fibers carrying out stretching radiation formation after simultaneously introduce a certain amount of allyl crosslinking agent and free radical scavenger in above-mentioned dry state gel precursor not only can make the superhigh molecular weight polyethylene fibers of formation have excellent heat resistance and creep resistance, and keeps the excellent properties such as the superelevation mechanical strength of this fibrid and ABRASION RESISTANCE.Superhigh molecular weight polyethylene fibers of the present invention is particularly useful for making bullet-proof vest and the helmet, lightweight armor, sail, hawser, fishing net, optical cable reinforcing body, parachute, filter material, radome, the wind power generation blade etc. of superelevation mechanical strength.
In one preferred embodiment, the weight average molecular weight rate of descent of the ultra-high molecular weight polyethylene caused due to radiation cleavage in crosslinked ultra-high-molecular-weight polyethylene fiber of the present invention is less than 10%, is preferably less than 8%.Preferably containing 0.05 ~ 5wt% free radical scavenger and 0.05 ~ 5wt% polymerization inhibitor in crosslinked ultra-high-molecular-weight polyethylene fiber of the present invention, with the weight of ultra-high molecular weight polyethylene for benchmark.Crosslinked ultra-high-molecular-weight polyethylene fiber of the present invention can at 110-120 DEG C of temperature aging 100 hours after-drawing strength retention ratio >90%, preferred >95%, more preferably >98%; Initial modulus retention rate >90%, preferred >95%; Reserved elongation at break is more than 80%, is preferably more than 90%.Rupture strength retention 70-95%, extension at break growth rate 5-15% after aging 300 hours at crosslinked ultra-high-molecular-weight polyethylene fiber of the present invention 110-120 DEG C of temperature.
The fiber number of crosslinked ultra-high-molecular-weight polyethylene fiber of the present invention is 50-3000dTex, is preferably 100-2500dTex, is more preferably 400 ~ 2000dTex.Its mechanical strength is 10-50cN/dTex, is preferably 15 ~ 45cN/dTex.
In one preferred embodiment, crosslinked ultra-high-molecular-weight polyethylene fiber infared spectrum of the present invention, compared with conventional commercial ultra-high molecular weight fibers, at 1687cm
-1a neighbouring appearance obvious peak, this peak is the characteristic peak (as C=C, C=O) of unsaturated bond in the crosslinking agent in the present invention, and the infrared light transmittance at this peak is more than 60%.
In one preferred embodiment, crosslinked ultra-high-molecular-weight polyethylene fiber of the present invention contains firm crosslinking agent, adopt the N element in elemental analyser mensuration crosslinking agent, N element content is 0.05 ~ 1wt% of supra polymer molecular weight cellulose, be preferably 0.1 ~ 0.5wt%, with the weight of ultra-high molecular weight polyethylene for benchmark.
Embodiment
By following embodiment, the present invention is described in detail, but the object of these embodiments only for explaining, and can not be used for limiting the scope of the invention.
In following embodiment, the various performances of crosslinked ultra-high-molecular-weight polyethylene fiber of the present invention such as can measure with the following method.
1) heat resistance
In 115 DEG C of baking oven air ambients after 100 hours aging, test crosslinked ultra-high-molecular-weight polyethylene tensile strength of fiber of the present invention and reserved elongation at break.
2) creep elongation
Tensile test method according to specifying in GBT 19975-2005 high-strength chemical-fibre filament draw method for testing performance is carried out, and wherein, load is 50% of fibrous fracture load, test temperature 70 DEG C.
3) gel content is according to gel content method of testing in ASTM D276-01 (2006) " gel content of cross-linked ethylene plastics and the standard method of test of swelling ratio ", adopts dimethylbenzene as solvent.
4) fiber number
According to the method test fibre number specified in GBT 19975-2005.
5) fracture strength
According to the method test fibrous fracture intensity specified in GBT 19975-2005.
6) elongation at break
According to the method test fibrous fracture percentage elongation specified in GBT 19975-2005.
7) infrared test
Test according to GBT 21186-2007 " Fourier transformation infrared spectrometer " method.
8) element test
Adopt German Elementa vario EL element test instrument, its combustion decomposition is made through catalytic oxidation in the oxygen atmosphere of sample at high temperature (1200-1800 DEG C), the non-detection gas generated in gas is removed, detected different component gas is by special adsorption column separation, re-use thermal conductivity detector (TCD) to detect respectively corresponding gas, helium is as carrier gas and sweep gas.
9) molecular weight and molecular weight rate test
The weight average molecular weight of superhigh molecular weight polyethylene fibers adopts ASTM D 4020 " standard declaration of ultra-high molecular weight polyethylene molding and extruded material " test.Before crosslinked, fiber molecule amount is M
0, after crosslinked, the molecular weight of fiber solubilized part is M
1, then the molecular weight and molecular weight rate D caused due to radiation degradation is:
D＝(M
1-M
0)/M
0×100％。
Embodiment 1
Take the ultra-high molecular weight polyethylene powder 3 weight portion (Gur 4022 of Ticona company, molecular weight ranges is 3,000,000), antioxidant 2,6-di-tert-butylphenol 0.003 weight portion, polarity modifier 2-phenoxyethyl acrylate 0.003 weight portion and dissolvant white oil 100 weight portion, be fully hybridly prepared into above-mentioned raw material the spinning solution that polyethylene concentration is 3wt%.At spinning equipment (for Jiangsu Shentai Technology Development Co., Ltd produces, spinning temperature: screw rod preheating zone: 60 ~ 110 DEG C, melting zone: 150 DEG C, metering zone: 160 DEG C, compressional zone: 170 DEG C, spin manifold temperature: 170 DEG C) on by spinning solution through Screw Extrusion spinning formed gel fiber, gel fiber at room temperature carries out predraft 1.2 times, adopt agent for carbon hydrogen detergent 103 to carry out extraction and form extraction silk, and two-stage drying is carried out to extraction silk, at 40 DEG C dry 10 minutes and at 80 DEG C dry 10 minutes respectively, the remaining extractant in removing extraction silk.Extraction silk contains the bath of cross-linking system solution by one with the speed of 1m/min, extraction silk time of staying in bath is 15 seconds.Crosslinker solution in this bath is by crosslinking agent, free radical scavenger, polymerization inhibitor and solvent composition, wherein the concentration of crosslinking agent trimethylol-propane trimethacrylate and three (2-ethoxy) isocyanuric acid triacrylate is respectively 2.5wt%, free radical scavenger 1,4-benzoquinone concentration 0.05wt%, polymerization inhibitor 2-TBHQ concentration is 0.04wt%, solvent is agent for carbon hydrogen detergent 103, with the weight of this solvent for benchmark.Extraction silk is made fully to absorb crosslinked agent and auxiliary agent thereof.Then by 4 grades of super times hot gas spring (the total multiplying power of drawing-off 45 times, drawing temperature controls at 120 ~ 160 DEG C, winding speed 45m/min), the fiber product of gained is through electron number cross-linking radiation (irradiation dose is 4Mrad).After radiation, the performance of fiber product is as shown in table 1.
Table 1
Comparative example 1
Take the ultra-high molecular weight polyethylene powder 3 weight portion (Gur 4022 of Ticona company, molecular weight ranges is 3,000,000), antioxidant 2,6-di-tert-butylphenol 0.003 weight portion and dissolvant white oil 100 weight portion, be fully hybridly prepared into above-mentioned raw material the spinning solution that polyethylene concentration is 3wt%.At spinning equipment (for Jiangsu Shentai Technology Development Co., Ltd produces, spinning temperature: screw rod preheating zone: 60 ~ 110 DEG C, melting zone: 150 DEG C, metering zone: 160 DEG C, compressional zone: 170 DEG C, spin manifold temperature: 170 DEG C) on by spinning solution through Screw Extrusion spinning formed gel fiber, gel fiber at room temperature carries out predraft 1.2 times, adopt agent for carbon hydrogen detergent 103 to carry out extraction and form extraction silk, and two-stage drying is carried out to extraction silk, at 40 DEG C dry 10 minutes and at 80 DEG C dry 10 minutes respectively, the remaining extractant in removing extraction silk.Extraction silk with the speed of 1m/min by containing cross-linking system solution bath, extraction silk time of staying in bath be 15 seconds.Cross-linking system solution in this bath is by crosslinking agent and solvent composition, wherein the concentration of crosslinking agent trimethylol-propane trimethacrylate and three (2-ethoxy) isocyanuric acid triacrylate is respectively 2.5wt%, solvent is agent for carbon hydrogen detergent 103, with the weight of solvent for benchmark.Extraction silk is made fully to absorb crosslinked agent and auxiliary agent thereof.Then by 4 grades of super times hot gas spring (the total multiplying power of drawing-off 45 times, drawing temperature controls at 120 ~ 160 DEG C, winding speed 45m/min), the fiber product of gained is through electron number cross-linking radiation (irradiation dose is 4Mrad).After radiation, the performance of fiber product is as shown in table 1.
Table 2
Embodiment 2
(super high molecular weight adopts the Gur4022 of Ticona company to take ultra-high molecular weight polyethylene powder 3 weight portion, molecular weight ranges is 4,000,000), antioxidant 2,6-di-tert-butylphenol and 4,4 '-thiobis (6-tertiary butyl-3-methylphenol) each 0.003 weight portion, polarity modifier laurate acrylate 0.003 weight portion and solvent mineral oil 100 weight portion.Above-mentioned raw material are fully hybridly prepared into the spinning solution that polyethylene concentration is 4wt%.At spinning equipment, (Jiangsu Shentai Technology Development Co., Ltd produces, spinning temperature: screw rod preheating zone: 60 ~ 110 DEG C, melting zone: 150 DEG C, metering zone: 160 DEG C, compressional zone: 170 DEG C, spin manifold temperature: 170 DEG C) on spinning solution is formed gel fiber through Screw Extrusion, gel fiber at room temperature carries out predraft 1.2 times, adopt dimethylbenzene to carry out extraction and form extraction silk, and two-stage drying is carried out to extraction silk, at 40 DEG C dry 10 minutes and at 80 DEG C dry 10 minutes respectively, the remaining extractant in removing extraction silk.Extraction silk is with the speed of 1m/min by the bath containing cross-linking system, and extraction silk time of staying in bath is 15 seconds.Cross-linking system solution in this bath is by crosslinking agent, free radical scavenger and solvent composition, wherein concentration 8wt%, the free radical scavenger 2 of crosslinking agent three (2-ethoxy) isocyanuric acid triacrylate, 2-diphenyl-1-trinitrophenyl-hydrazine concentration 0.05wt%, solvent is agent for carbon hydrogen detergent 104, with the weight of this solvent for benchmark.Extraction silk is made fully to absorb crosslinked agent and auxiliary agent thereof.Then by 4 grades of super times hot gas spring (the total multiplying power of drawing-off 40 times, drawing temperature controls at 120 ~ 160 DEG C, winding speed 45m/min), gained fibre is through electron number cross-linking radiation, and irradiation dose is 2Mrad.After radiation, the performance of fibre is as shown in table 3.
Table 3
Embodiment 3
(super high molecular weight adopts the Gur4022 of Ticona company to take ultra-high molecular weight polyethylene powder 3 weight portion, molecular weight ranges is 5,000,000), antioxidant 1010 is 0.01 weight portion, antioxidant 4,4 '-thiobis (6-tertiary butyl-3-methylphenol) 0.006 weight portion, polarity modifier ring trimethylolpropane acetal acrylate 0.003 weight portion and solvent mineral oil 100 weight portion.Above-mentioned raw material are fully hybridly prepared into the spinning solution that polyethylene concentration is 3wt%.At spinning equipment (for Jiangsu Shentai Technology Development Co., Ltd produces, spinning temperature: screw rod preheating zone: 60 ~ 110 DEG C, melting zone: 150 DEG C, metering zone: 160 DEG C, compressional zone: 170 DEG C, spin manifold temperature: 170 DEG C) on above-mentioned spinning solution is formed gel fiber through Screw Extrusion, gel fiber at room temperature carries out predraft 1.2 times, adopt No. 120 gasoline to carry out extraction and form extraction silk, and two-stage drying is carried out to extraction silk, at 40 DEG C dry 10 minutes and at 80 DEG C dry 10 minutes respectively, the remaining extractant in removing extraction silk.Extraction silk with the speed of 1m/min by containing cross-linking system bath, extraction silk time of staying in bath be 15 seconds.Cross-linking system solution in this bath is by crosslinking agent, free radical scavenger, polymerization inhibitor and solvent composition, wherein the concentration of crosslinking agent triallyl isocyanuric acid ester and ethoxyquin trimethylolpropane triacrylate is respectively 4wt%, free radical scavenger tetramethyl-benzoquinone concentration 0.05wt%, polymerization inhibitor MEHQ concentration is 0.04wt%, solvent is agent for carbon hydrogen detergent 104, with the weight of this solvent for benchmark.Then by 4 grades of super times hot gas spring (the total multiplying power of drawing-off 50 times, drawing temperature controls at 120-160 DEG C, winding speed 50m/min), carry out gamma-ray irradiation to the fibre of gained and be cross-linked, irradiation dose is 8Mrad.After radiation, the performance of fiber product is as shown in table 4:
Table 4
Embodiment 4
Take ultra-high molecular weight polyethylene powder 3 weight portion (Gur 4022 of Ticona company, molecular weight ranges is 4,500,000), antioxidant 1010 is 0.01 weight portion, antioxidant tricresyl phosphite different monooctyl ester 0.005 weight portion, polarity modifier oxolane acrylate 0.003 weight portion and solvent paraffin oil 100 weight portion.Above-mentioned raw material are fully hybridly prepared into the spinning solution that polyethylene concentration is 5wt%.At spinning equipment (for Jiangsu Shentai Technology Development Co., Ltd produces, spinning temperature: screw rod preheating zone: 100 DEG C, melting zone: 160 DEG C, metering zone: 170 DEG C, compressional zone: 180 DEG C, spin manifold temperature: 190 DEG C) on by above-mentioned spinning solution through Screw Extrusion spinning formed gel fiber, gel fiber at room temperature carries out predraft 1.5 times, adopt carrene to carry out extraction and form extraction silk, and two-stage drying is carried out to extraction silk, at 40 DEG C dry 10 minutes and at 80 DEG C dry 10 minutes respectively, the remaining extractant in removing extraction silk.Extraction silk is with the speed of 1m/min by the bath containing cross-linking system, and extraction silk time of staying in bath is 15 seconds.Cross-linking system solution in this bath is by crosslinking agent, free radical scavenger, polymerization inhibitor and solvent composition, wherein the concentration of crosslinking agent triallyl isocyanuric acid ester and propylene glycol diacrylate is respectively 3wt%, free radical scavenger 2,2-diphenyl-1-trinitrophenyl-hydrazine concentration 0.05wt%, polymerization inhibitor 2,6-di-t-butyl-4 (dimethyl aminomethyl phenol) concentration is 0.04wt%, solvent is agent for carbon hydrogen detergent 104, with the weight of this solvent for benchmark.Extraction silk is made fully to absorb crosslinked agent and auxiliary agent thereof, then by 4 grades of super times hot gas spring (the total multiplying power of drawing-off 45 times, drawing temperature controls at 130 ~ 150 DEG C, winding speed 45m/min), the fibre of gained is through electron beam to irradiate crosslinked, and irradiation dose is 8Mrad.After radiation, the performance of fiber product is as shown in table 5.
Table 5
Embodiment 5
Take ultra-high molecular weight polyethylene powder 3 weight portion (adopt the Gur 4022 of Ticona company, molecular weight ranges is 2,500,000), antioxidant 1010 is 0.01 weight portion, antioxidant triphenyl phosphite 0.006 weight portion, polarity modifier iso-bornyl acrylate 0.003 weight portion and solvent naphthane 100 weight portion.Above-mentioned raw material are fully hybridly prepared into the spinning solution that polyethylene concentration is 8wt%.At spinning equipment (for Jiangsu Shentai Technology Development Co., Ltd produces, spinning temperature: screw rod preheating zone: 100 DEG C, melting zone: 160 DEG C, metering zone: 170 DEG C, compressional zone: 180 DEG C, spin manifold temperature: 190 DEG C) above-mentioned spinning solution is formed gel fiber through Screw Extrusion spinning, gel fiber at room temperature carries out predraft 1.5 times, adopt tetrachloro-ethylene to carry out extraction and form extraction silk, and two-stage drying is carried out to extraction silk, at 40 DEG C dry 10 minutes and at 80 DEG C dry 10 minutes respectively, the remaining extractant in removing extraction silk.Extraction silk is with the speed of 1m/min by the bath containing cross-linking system, and extraction silk time of staying in bath is 15 seconds.Cross-linking system solution in this bath is by crosslinking agent, free radical scavenger, polymerization inhibitor and solvent composition, crosslinking agent triallyl cyanuric acid ester concentration 3wt%, light trigger benzophenone and 4-methyl benzophenone concentration are respectively 3wt%, free radical scavenger phenyl-N-tert-butylnitrone concentration 0.05wt%, polymerization inhibitor methylnaphthohydroquinone is 0.04wt%, solvent is agent for carbon hydrogen detergent 104, with the weight of this solvent for benchmark.Then by 4 grades of super times hot gas spring (the total multiplying power of drawing-off 40 times, drawing temperature controls at 130 ~ 150 DEG C, winding speed 40m/min), the fibre of gained is cross-linked through ultraviolet irradiation, and exposure time is 10s.After radiation, the performance of fiber product is as shown in table 6.
Table 6
Claims (10)
1. a crosslinked superhigh molecular weight polyethylene fibers, the weight average molecular weight rate of descent of the ultra-high molecular weight polyethylene wherein caused due to radiation or irradiation to crack is less than 10%.
2. crosslinked ultra-high-molecular-weight polyethylene fiber as claimed in claim 1, it is characterized in that, the initial weight average molecular weight of described superhigh molecular weight polyethylene fibers is 100-1000 ten thousand, be preferably 250-700 ten thousand, described superhigh molecular weight polyethylene fibers contains 0.05 ~ 5wt% free radical scavenger, with the weight of ultra-high molecular weight polyethylene for benchmark.
3. crosslinked ultra-high-molecular-weight polyethylene fiber as claimed in claim 1 or 2, it is characterized in that, its mechanical strength is 15 ~ 45cN/dTex.
4. crosslinked ultra-high-molecular-weight polyethylene fiber as claimed in claim 1 or 2, it is characterized in that, high in the degree of cross linking of the cross section upper periphery part of described fiber, the degree of cross linking of core is low, described crosslinked be the crosslinking with radiation under allyl crosslinking agent exists.
5. crosslinked ultra-high-molecular-weight polyethylene fiber as claimed in claim 1 or 2, it is characterized in that, the average fineness of described fiber is 50-3000dTex, is preferably 400 ~ 2000dTex.
6. the preparation method of the crosslinked ultra-high-molecular-weight polyethylene fiber according to any one of claim 1-5, it comprises the steps:
1) ultra-high molecular weight polyethylene spinning solution is provided;
2) spray silk by described spinning solution and form hygrometric state gel precursor;
3) use extractant to extract described hygrometric state gel precursor, form extraction silk;
4) the extraction silk described in drying, removing extractant, obtains dry state gel precursor;
5) allow dry state gel precursor by one or more bath, make dry state gel precursor absorption cross-linking system body lotion wherein, cross-linking system body lotion contains allyl crosslinking agent and free radical scavenger;
6) at the temperature of 90-180 DEG C, the dry state gel precursor absorbing body lotion is drawn one or more additional times; With
7) the dry state gel precursor after stretching is cross-linked, preferably drawing-off or tension force HEAT SETTING again after cross-linking.
7. preparation method as claimed in claim 6, is characterized in that, also containing polarity modifier, fiber antioxidant and low voc solvent in described ultra-high molecular weight polyethylene spinning solution.
8. preparation method as claimed in claims 6 or 7, it is characterized in that, described allyl crosslinking agent is selected from triallyl isocyanuric acid ester, triallyl cyanurate, trimethylol-propane trimethacrylate, ethoxyquin trimethylolpropane triacrylate, glycerol propoxylate triacrylate, three (2-ethoxy) isocyanuric acid triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, 1, 6-hexanediyl ester, ethoxylated bisphenol A diacrylate, dimethacrylate, propylene glycol diacrylate, polyethyleneglycol diacrylate or their mixture, described free radical scavenger is selected from 2, 2-diphenyl-1-trinitrophenyl-hydrazine, 1,4-benzoquinone, tetramethyl-benzoquinone, 2-methyl-2-nitromethane, phenyl-N-tert-butylnitrone or their mixture.
9. preparation method as claimed in claims 6 or 7, it is characterized in that, described cross-linking system solution contains 1-30wt% allyl crosslinking agent, 0.01-1wt% free radical scavenger and 0-1wt% polymerization inhibitor, with the weight of extractant for benchmark, described polymerization inhibitor is selected from 2,5-di-tert-butyl hydroquinone, 2-TBHQ, MEHQ, methylnaphthohydroquinone, hydroquinones, 2,6-di-t-butyl-4 (dimethyl aminomethyl phenol) or their mixtures.
10. preparation method as claimed in claims 6 or 7, is characterized in that, is 0.01-35Mrad, is preferably 5-18Mrad to the irradiation dose of the dry state gel precursor after stretching.
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