A kind of manufacture method of high elongation at tear Fanglun 1414Technical field
The present invention relates to a kind of manufacture method of fiber, it is more particularly related to a kind of high elongation at tear is poly-The manufacture method of poly P phenylene diamine terephthalamide fiber, belongs to staple fibre technical field.
Background technology
PPTA（PPTA）Fiber adopts Low-temperature Solution Polycondensation in nineteen sixty-five by du pont companyIt is synthesized, then using PPTA/H2SO4Solution has liquid crystal behavior, has invented the method for dry-jet wet-spinning, so as to obtain high propertyCan Fanglun 1414（Referred to as " Fanglun l414 "）.The patent of correlation technique exists successively in 1970-1985The U.S. delivers, for example the patent No.：3671542、3819587、19730361818、3767756、3869429、3849430、4726922nd, 5001219,5009830,19760720849,19880182826,1980012088,19970950250 etc..
Du pont company carries out PPTA fiber productions from the developing target market that 1972 start small lot, nineteen eighty-two start intoRow industrialized production, name of product is Kevlar.Holland Akzo input PPTA aramid fibers are produced within 1985, and name of product isTwaron.Japanese Di Ren companies merge the Twaron business of Akzo companies of Holland for 2005, and it is public with Du Pont persistently to expand yieldDepartment's competition.Also in test manufacture PPTA in 1985 and pulp, the production is basic from 1990 to 2000 years to be stopped Ke Long companies of Korea, inRecover development from 2006 and found the factory.
Fanglun l414 fiber product has various commercial varieties, for comprehensive international market commodity, is broadly divided into following severalClass：
1. general Fanglun l414 fiber.By force in 22-23g/d scopes, elongation 2.5-3.6%, modulus is about 550g/ to its long filamentD, this product is mostly used for the applications such as spinning, friction material.
2. high modulus product in Fanglun l414.Its filament modulus is more than 750g/d, and this product is mostly used for optical cable benefitBy force, the application such as composite reinforcement.
3. high intensity Fanglun l414 fiber product, its more than yarn strength 26g/d, are used for shellproof military use.
4. Fanglun l414 fiber product is activated, is mainly used in rubber compounding art.
The main physical and chemical performance of PPTA polymer includes-NH or-CO end group, the molecule of strandAmount, molecular weight distribution, density, moisture content, decomposition temperature, particle diameter, ash etc., these indexs can all produce shadow to fibre propertyRing, wherein polymer molecular weight size directly affects the mechanical property of fiber, including fracture strength, modulus and elongation at break,But, this index is very difficult to directly measure, and log viscosities are usually used as technical indicator, is more beneficial for quick grasp and gathersThe physical property infomation of poly P phenylene diamine terephthalamide polymer and its fiber, fully reflects Fanglun l414 polymerization, the technology of spinningRoute and technological level.
The molecular weight for directly determining PPTA is extremely difficult, but can be viscous using its dilution heat of sulfuric acidDegree is made to indicate indirectly, general to adopt " log viscosities "（inherent viscosity）, it is defined as follows：
ηinh= ln ηrel/C
η in formulainhThat is log viscosities, ηrelThe ratio of viscosity and solvent viscosity for relative viscosity, i.e. polymer solution, C isThe polymer concentration of solution.The measure of the log viscosities of PPTA is that in the 96-98% concentrated sulfuric acids, taking C is0.5g/dL, measures in the case where temperature is for 30 DEG C.
The performance of polymer molecular weight effects its derivatives, manufacture Fanglun l414 fiber is same, molecular weight effects fiberPerformance, especially mechanical property, such as fibre strength and modulus.Molecular weight is too low, poor mechanical property, manufactures when molecular weight is too highThe technique of fiber is extremely difficult, and yield is very low, affects industrial efficiency and production cost.
PPTA polymer does not have fusing point, it is impossible to adopt melt spinning.Spinning generally acknowledged in the industry at presentSilk mode is dry-jet wet-spinning（dry-jet wet spinning）, will PPTA polymer be dissolved in dense sulphurAcid, its concentration can form liquid crystal aligning solution in 12-19.6%（Anisctropic Solution）, referred to as spin slurry.WillThis solution carries out in coagulating bath again mass exchange after spinneret, after air setting, separates out the sulfuric acid spun in slurry,Prepared high-performance fiber.The process characteristic of dry-jet wet-spinning is：Spinneret is located at coagulating bath top during spinning, between solidification liquid levelAir lamellar spacing with certain altitude.Under slurry is spun by spinneret spray, through air layer, into coagulating bath, derive from solidification pipe.The thread spinning sprayed from spinneret is starched and liquid extraction is being solidified when coagulating bath, and polymer precipitates into fiber, most ofSulfuric acid diffuses into solidification liquid.The spun filament that solidification is obtained is wound into fiber product Jing after the technique such as washing, neutralization, dry.
Technique in the preparation of PPTA polymer and dry-jet wet-spinning and fiber last handling processDifference, can prepare the different differential Fanglun l414 product of fibre property.
PPTA is a kind of straight chain molecule, and molecules align is regular, therefore by poly- paraphenylene terephthalamide coupleFanglun l414 fiber rigidity prepared by phenylenediamine is very strong, and modulus itself is very high, and elongation at break is with respect to other flexible molecule materialsIt is low.Fibrous material used in automobile tire official hats and canopies layer cord fabric thread, needs the fatigue for overcoming Tire High Frequency rate to roll, that is, needHigher anti-disc fatigue performance, it is necessary to higher elongation at break.In belt applications, aramid fiber first has to establishmentInto canvas, then as the framework material of conveyer belt, resist bending and compression and fatigue resisting performance are needed also exist for.This resist bending and resistance toProperty of compression fatigue needs the elongation at break for improving material, and the performance of the high-strength low-density of this material of Fanglun l414 is veryIt is adapted to be applied in tire and conveyer belt, can significantly mitigates the weight of tire and conveyer belt, but, the aramid fiber of common model1414 elongation at breaks are usually less than 3.6%, are not suitable for using in these areas.
China is the big producing country of rubber first, hundred million yuan of annual value of production 4000-5000.The overall speedup of rubber industry is bigIn China's GDP speedups, before financial crisis in 2008, the average speedup of the industry such as sebific duct, adhesive tape, radial is 25%Left and right.Except consuming a large amount of rubber (about 6,000,000 tons) every year, framework material (including polyamide fibre, terylene, steel wire etc.) is also rubber workThe important basic material of industry, consumption is very big.All kinds of rubber framework materials of China are concentrated on traditional material, new and high technology materialThe few application of material：The remarkable aramid fiber of the such as fiber of polyamide fibre 46, para-aramid fiber, PEN fibers, carbon fiber, especially performance is fineDimension, the application in China's rubber industry is not popularized in an all-round way, as long as applying on a small quantity in the knitting special-shaped sebific duct of aramid fiber and automobileOn cutting transmission belt.
According to foreign statistic, the aramid fiber for being applied to the rubber products such as tire and glue tube belt accounts for the 20% of total consumption, rubberGlue industry is the second largest field of aramid fiber application.Global aramid fiber is applied in the t of the Rubber Industry about 1.5-2.0 ten thousand (whole worldAramid fiber yield about 100,000 t), China only less than 500 tons, its main cause：1. high-performance fiber is still by external monopolization, and price is high,Product type is limited, therefore limits application；2. autonomous composite core technology is lacked.
The content of the invention
Present invention seek to address that Fanglun 1414's elongation at break of the prior art is with respect to otherFlexible molecule material is low, and elongation at break is usually less than 3.6%, and it is received in some applications for needing the field of high elongation at tearTo the problem for affecting, there is provided a kind of manufacture method of high elongation at tear Fanglun 1414, party's legal systemThe Fanglun 1414 for creating has high elongation at tear, it is adaptable to which industrial scale is produced, with excellentGood shock resistance and anti-fatigue performance, are relatively specific for conveyer belt and tire art.
In order to realize foregoing invention purpose, its specific technical scheme is as follows：
A kind of manufacture method of high elongation at tear Fanglun 1414, it is characterised in that：With log viscositiesThe PPTA polymer of 4.5-7.5dl/g is raw material, with the 96-100% concentrated sulfuric acids as solution, makes spinningAfter stoste, using dry-jet wet spinning process, nascent strand is formed by spinneret, subsequently into coagulating bath solidification forming, be frozen intoThe fiber of shape passes through washing, neutralization, is dried and oils, and is wound into product, wherein in washing, neutralizing, being dried, oil and roll upDuring, spinline tension is controlled in below 0.5g/d.
Currently preferred, the log viscosities of the PPTA polymer raw material are 6.0-6.5dL/g。
Currently preferred, the spinning solution is obtained by following methods：By the log viscosities 4.5-7.5 dL/g'sDuring PPTA polymer adds concentration for the sulfuric acid of 96-100%, by strong in double-screw reactor78-82 DEG C is stirred and be warming up to, the spinning solution that concentration is 19.0-19.5% is made.
Currently preferred, the inherent viscosity of the spinning solution is more than 4.5dl/g and needs to carry out secondary filter, removesGel particle and solid insoluble particle, filtering accuracy is less than 10 microns.
It is currently preferred, the orifice diameter≤0.065mm of the spinneret.
Currently preferred, the spinning speed in the dry-jet wet spinning process is 200-750m/min.
Currently preferred, flow of the solidification liquid in the dry-jet wet spinning process in solidification pipe is 200-400kg/h,The internal diameter 6-10mm of solidification pipe.
The Advantageous Effects that the present invention brings：
1st, the present invention, by controlling spinning process tension force≤0.05mm, by control slurry is spun in the spinning process of dry-jet wet-spinningCharacteristic, the tension force in coagulation forming process and washing dry run is obtained with poly- to benzene two more than 3.6% elongation at breakFormyl p-phenylenediamine fiber.The fiber has excellent impact resistance and fatigue performance, is relatively specific for rubber composite neckDomain and ballistic composite.
3rd, the present invention is moderate to aramid fiber polymeric compound viscosity requirement, with versatility.The present invention adopts log viscosities for 4.5-The polymer of 7.5dL/g, asks its moderate, on the one hand avoids difficulty in polymerization, with slurry and spinning operation, on the one hand ensures that gained is fineDimension has excellent properties, and process efficiency is high, industrializes low cost.
4th, the specific targets of the Fanglun 1414 include：Tow fineness is 200-3000dan, intensity21-30g/d, elongation at break 2.5-4.4%, modulus 500-900g/d, moisture content 4-10%, fiber log viscosities 4.5-7.5dl/g.The method can prepare the fiber in the range of elongation at break 2.5-4.4%, when high elongation at tear is needed, Ke YizhiThe fiber prepared higher than 3.6% elongation at break is connect, for conveyer belt and tire art.
5th, currently preferred, the inherent viscosity of the spinning solution is more than 4.5dl/g and needs to carry out secondary filter, goesExcept gel particle and solid insoluble particle, filtering accuracy is less than 10 microns.The filtration essence that the present invention passes through control spinning solutionDegree, can effectively filter out gel particle and solid insoluble particle, because spinning spinneret plate aperture is very little, it is therefore desirable toLarger insoluble particle is all removed, just can guarantee that it is continuous, fibre structure defect that slurry slice is spun in spinning processIt is few, form finer and close structure, more regular arrangement, so as to possess the fiber for obtaining high elongation rate.
6th, currently preferred, the log viscosities of the PPTA polymer raw material are 6.0-6.5dL/g.The interval polymer of preferred log viscosities, first, it is smaller that this interval polymer prepares difficulty, it is not necessary toEspecially complex or harsh reaction condition；Second, this interval polymer spin slurry prepare when be easier, prevent due toDegradation speed is fast, and so as to affect fibre strength and modulus, the spinning slurry that it also avoid configuring is uneven, easily containing more gelParticle, so as to affect to spin the spinnability of slurry.
7th, currently preferred, the spinning solution is obtained by following methods：By the log viscosities 4.5-7.5 dL/gPPTA polymer add concentration for the sulfuric acid of 96-100%, by strong in double-screw reactorStrong stirring is simultaneously warming up to 78-82 DEG C, makes the spinning solution that concentration is 19.0-19.5%.Under control said temperature, polymer was bothCan well be dissolved, will not be degraded because of temperature is too high again.Under concentration 19.0-19.5% state, spin slurry presentation and set outThe minimum mesomorphic state of power viscosity, spinnability is best.
8th, it is currently preferred, the orifice diameter≤0.065mm of the spinneret.The reasonable virtue of usual mechanical propertyThe single fiber 1.5D of synthetic fibre fiber, 12 microns of diameter.Spin plate orifice diameter it is bigger, spin plate spinneret orifice and final fibre diameter itBetween ratio it is bigger, that is, represent fiber from spin plate start it is bigger to the stretch ratio of final fiber.Excessive draw ratioFibre structure defect can be caused, therefore, select orifice diameter≤0.065mm.
9th, currently preferred, the spinning speed in the dry-jet wet spinning process is 200-750m/min.Spinning speed is got overLow, lower to spinning equipment requirement, the fibrous mechanical property of acquisition is better, but spinning efficiency is lower.200-750m/min was bothCan guarantee that spinning efficiency can guarantee that the speed interval of fibre property again.
10th, currently preferred, flow of the solidification liquid in the dry-jet wet spinning process in solidification pipe is 200-400kg/h, solidifies the internal diameter 6-10mm of pipe.The fiber of higher mechanical property can be obtained under above-mentioned process conditions.
Specific embodiment
Embodiment 1
A kind of manufacture method of high elongation at tear Fanglun 1414, it is characterised in that：With log viscositiesThe PPTA polymer of 4.5dl/g is raw material, with 96% concentrated sulfuric acid as solution, after making spinning solution, is adoptedWith dry-jet wet spinning process, nascent strand is formed by spinneret, subsequently into coagulating bath solidification forming, the fiber Jing of solidification formingWashing, neutralization are crossed, is dried and is oiled, be wound into product, wherein in washing, neutralization, the process for being dried, oiling and windIn, spinline tension is controlled in 0.1g/d.
Embodiment 2
A kind of manufacture method of high elongation at tear Fanglun 1414, it is characterised in that：With log viscositiesThe PPTA polymer of 7.5dl/g is raw material, with 100% concentrated sulfuric acid as solution, after making spinning solution,Using dry-jet wet spinning process, nascent strand is formed by spinneret, subsequently into coagulating bath solidification forming, the fiber of solidification formingThrough washing, neutralize, be dried and oil, be wound into product, wherein in washing, neutralization, the process for being dried, oiling and windIn, spinline tension is controlled in 0.5g/d.
Embodiment 3
A kind of manufacture method of high elongation at tear Fanglun 1414, it is characterised in that：With log viscositiesThe PPTA polymer of 6dl/g is raw material, with 98% concentrated sulfuric acid as solution, after making spinning solution, is adoptedDry-jet wet spinning process, by spinneret nascent strand is formed, and subsequently into coagulating bath solidification forming, the fiber of solidification forming is passed throughWashing, neutralization, be dried and oil, be wound into product, wherein washing, neutralization, be dried, oil and wind during,Spinline tension is controlled in 0.3g/d.
Embodiment 4
A kind of manufacture method of high elongation at tear Fanglun 1414, it is characterised in that：With log viscositiesThe PPTA polymer of 5dl/g is raw material, with 99% concentrated sulfuric acid as solution, after making spinning solution, is adoptedDry-jet wet spinning process, by spinneret nascent strand is formed, and subsequently into coagulating bath solidification forming, the fiber of solidification forming is passed throughWashing, neutralization, be dried and oil, be wound into product, wherein washing, neutralization, be dried, oil and wind during,Spinline tension is controlled in 0.4g/d.
Embodiment 5
On the basis of embodiment 1-4：
Preferably, the log viscosities of the PPTA polymer raw material are 6.0dL/g.
Preferably, the spinning solution is obtained by following methods：By the poly- paraphenylene terephthalamide of the log viscosities 4.5dL/gP-phenylenediamine polymer adds the concentration to be in 96% sulfuric acid, and by strong agitation and 78 DEG C are warming up in double-screw reactor,Make the spinning solution that concentration is 19.0%.
Preferably, the inherent viscosity of the spinning solution is more than 4.5dl/g and needs to carry out secondary filter, removes gelGrain and solid insoluble particle, filtering accuracy is less than 10 microns.
Preferably, the orifice diameter≤0.065mm of the spinneret.
Preferably, the spinning speed in the dry-jet wet spinning process is 200m/min.
Preferably, flow of the solidification liquid in the dry-jet wet spinning process in solidification pipe is 200kg/h, solidifies the interior of pipeFootpath 6mm.
Embodiment 6
On the basis of embodiment 1-4：
Preferably, the log viscosities of the PPTA polymer raw material are 6.5dL/g.
Preferably, the spinning solution is obtained by following methods：By the poly- paraphenylene terephthalamide of the log viscosities 7.5dL/gP-phenylenediamine polymer adds the concentration to be in 100% sulfuric acid, and by strong agitation and 82 are warming up in double-screw reactorDEG C, make the spinning solution that concentration is 19.5%.
Preferably, the inherent viscosity of the spinning solution is more than 4.5dl/g and needs to carry out secondary filter, removes gelGrain and solid insoluble particle, filtering accuracy is less than 10 microns.
Preferably, the orifice diameter≤0.065mm of the spinneret.
Preferably, the spinning speed in the dry-jet wet spinning process is 750m/min.
Preferably, flow of the solidification liquid in the dry-jet wet spinning process in solidification pipe is 400kg/h, solidifies the interior of pipeFootpath 10mm.
Embodiment 7
On the basis of embodiment 1-4：
Preferably, the log viscosities of the PPTA polymer raw material are 6.25dL/g.
Preferably, the spinning solution is obtained by following methods：By the poly- paraphenylene terephthalamide couple of the log viscosities 6dL/gIt is in 98% sulfuric acid, strong agitation to be passed through in double-screw reactor and 80 DEG C are warming up to that phenylenediamine polymer adds concentration, systemInto the spinning solution that concentration is 19.25%.
Preferably, the inherent viscosity of the spinning solution is more than 4.5dl/g and needs to carry out secondary filter, removes gelGrain and solid insoluble particle, filtering accuracy is less than 10 microns.
Preferably, the orifice diameter≤0.065mm of the spinneret.
Preferably, the spinning speed in the dry-jet wet spinning process is 475m/min.
Preferably, flow of the solidification liquid in the dry-jet wet spinning process in solidification pipe is 300kg/h, solidifies the interior of pipeFootpath 8mm.
Embodiment 8
On the basis of embodiment 1-4：
Preferably, the log viscosities of the PPTA polymer raw material are 6.2dL/g.
Preferably, the spinning solution is obtained by following methods：By the poly- paraphenylene terephthalamide couple of the log viscosities 5dL/gIt is in 99% sulfuric acid, strong agitation to be passed through in double-screw reactor and 81 DEG C are warming up to that phenylenediamine polymer adds concentration, systemInto the spinning solution that concentration is 19.3%.
Preferably, the inherent viscosity of the spinning solution is more than 4.5dl/g and needs to carry out secondary filter, removes gelGrain and solid insoluble particle, filtering accuracy is less than 10 microns.
Preferably, the orifice diameter≤0.065mm of the spinneret.
Preferably, the spinning speed in the dry-jet wet spinning process is 700m/min.
Preferably, flow of the solidification liquid in the dry-jet wet spinning process in solidification pipe is 220kg/h, solidifies the interior of pipeFootpath 9mm.
Embodiment 9
The comparison of the typical physical performance of product of the present invention and similar aramid fiber II products is as shown in table 1：
Table 1：The typical physical Performance comparision of this product and similar aramid fiber II products
Embodiment 10
A kind of high elongation rate PPTA（PPTA）The manufacture method of fiber, it is characterised in that：It is viscous with logarithmThe PPTA of degree 6.5dL/g（PPTA）Polymer is raw material, and by the spinning process in dry-jet wet-spinningIn specially treated be prepared from, the specific targets of the poly P phenylene diamine terephthalamide fiber include：Beam yarn fiber number 3000D, by forceDegree 25g/d, elongation at break 4%, modulus 475g/d, moisture content 5%, log viscosities 6.2dL/g.
The employing Low-temperature Solution Polycondensation method is prepared with regard to poly P phenylene diamine terephthalamide（PPTA）The concrete step of polymerIt is rapid as follows：
（1）The preparation of aramid fiber polymeric compound
The primary raw material that aramid fiber polymeric compound is adopted is p-phenylenediamine（p-phenylene diamine）[PPD] and paraphenylene terephthalamideChlorine（Terephthaloyl chloride）[TPC], polymer solvent is 1-METHYLPYRROLIDONE [NMP], helps polysalt to be calcium chloride[CaCl2]；Wherein, the mol ratio of PPD/TPC is equal to 0.995-1.015, and the mol ratio of CaCl2/PPD is equal to 1.2-1.7, polymerizationThe solid content of mixture is 9.0-12%.
Polymerisation, two-step process are carried out using double-screw reactor.First, by p-phenylenediamine [PPD], N- methyl pyrrolesPyrrolidone [NMP], helps polysalt calcium chloride [CaCl2] to carry out being sufficiently mixed dissolving；Then again in pre-polymerization reactor with it is a certain amount ofParaphthaloyl chloride TPC carry out polycondensation reaction, form prepolymer, the wherein mol ratio of TPC/PPDA is equal to 0.25-0.65；Prepolymer carries out second polymerisation with TPC in double-screw reactor, the institute in pre-polymerization and second polymerization processThe total amount of the TPC of addition should be equimolar with the total amount of PPDA.
Contain solvent, auxiliary agent and the HCL for generating in the polymer that polymerisation is obtained.By with sodium hydroxide solution pairPolymer is neutralized washing and is dried.The polymer of clean dry is finally given, the moisture of polymer needs control 0.5%Within, other possible total impurities are no more than 50PPM.
（2）The preparation of spinning solution
The polymer of clean dry is mixed with the concentrated sulfuric acid and is stirred, and forms liquid crystalline solution, i.e. spinning solution.It is usually usedDouble-screw reactor completes the preparation of spinning solution, and solid content of the polymer in liquid crystal solution should be controlled between 16%-22%.Spinning solution is delivered to spinning pump after deaeration and filtration.The filtering accuracy of filter should be controlled below 10 microns,Guarantee that insoluble impurity and gel particle are filtered completely.The spinning solution of preparation needs to carry out spinning in time, and holding process is notCan exceed that 4 hours, will otherwise cause viscosity to decline, so as to affect fibre property.
（3）Spinning
Including solidification, extraction, spinning, washing, neutralization, drying, the operation such as oil, wind.
By the dL/g PPTAs of above-mentioned log viscosities 6.5（PPTA）Polymer, add concentration beIn 99.8% sulfuric acid, through strong agitation and be warming up to 81 DEG C, make the spinning slurry that concentration is 19.35%, slurries after filtering byAfter gear wheel metering pump from spinneret spray, the hole diameter of spinneret≤0.065mm, spin slurry spray spin hole after slurry silk, it is empty through 6mmGas-bearing formation, into coagulation system, the solidification pipe through solidifying groove center, flows out from pipe is lower.0-10 DEG C of coagulation bath temperature, solidification liquidAcid content 10%, sulfuric acid contained in spinning slurry becomes vitriolated wet yarn by partial extraction after solidification pipe；Wet yarnContinue to carry out washing, neutralization of the order for washing/alkali cleaning/alkali cleaning on multistage rotating cylinder, then do on 135 DEG C of drying drumsIt is dry.Wet yarn is in washing/alkali cleaning/alkali cleaning/drying until in winding process, controlling roller speed.The speed of rear stage roller is biggerIn the speed of previous stage roller, spinning tension is formed, make fiber that tensioned state is kept in overall process, while controlling spinning tensionAs far as possible little, fiber not Tensile in this process forms fine and close regular molecular structure, so as to obtain high elongation rate, this mistakeTension force in journey should be controlled in 0-0.5g/d.Dry yarn oils and wound on paper web with up- coiler after arranging, and winding speed is500m/min。
The long yarn performance of gained is listed in table 2
Table 2：Aramid fiber key property