CN103469343B - A kind of method improving the Interaction Force of fento in aramid fiber - Google Patents
A kind of method improving the Interaction Force of fento in aramid fiber Download PDFInfo
- Publication number
- CN103469343B CN103469343B CN201310419323.XA CN201310419323A CN103469343B CN 103469343 B CN103469343 B CN 103469343B CN 201310419323 A CN201310419323 A CN 201310419323A CN 103469343 B CN103469343 B CN 103469343B
- Authority
- CN
- China
- Prior art keywords
- ppta
- fento
- fiber
- spinning
- aramid fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Artificial Filaments (AREA)
Abstract
The present invention relates to a kind of method improving the Interaction Force of fento in aramid fiber, it is a kind of liquid crystal property that can ensure fluid by micro-copolymerization, the spin fluid with certain confusion degree can be obtained again, in spinning process, form the preparation method having interactional fiber between fento.The failure mode of aramid fiber is the slippage of fento, therefore improves the mechanical property of aramid fiber, should improve the interaction between fento.It is control due to the phase in version in fiber spinning from crystalline state process of setting that fento between aramid fiber interacts.Trace copolymerization does not change the process of liquid crystal behavior and fiber spinning from crystalline state, by destroying the regularity between liquid crystal molecule chain, increases the confusion degree of liquid crystal.The crystallite with certain randomness changes the interaction of fento, and the strength and modulus of fiber is improved.This method is easy, can obtain stablizing, the aramid fiber that mechanical property is good by dry spray-wet method fiber spinning from crystalline state method of forming.
Description
Technical field
The present invention relates to a kind of method improving the Interaction Force of fento in aramid fiber, it is a kind of liquid crystal property that can ensure fluid by micro-copolymerization, the spin fluid with certain confusion degree can be obtained again, in spinning process, form the preparation method having interactional fiber between fento, belong to the spining technology field of aramid IIII fiber.
Background technology
P-aramid fiber, i.e. Fanglun 1414's (being called for short PPTA), due to the high symmetry of strand, regularity and rigid structure, therefore there is the excellent mechanical property such as high strength, high-modulus and low-density, high-dimensional stability, the high temperature resistant advantage such as good.
But PPTA resin indissoluble infusibility, must carry out fiber spinning from crystalline state, complex process in concentrated sulfuric acid, the resistance to strong acid corrosion of equipment requirement, processes more difficult.And easy crystallization after spinning moulding, reduce the tensility of fiber.And add comonomer and carry out copolycondensation, improve its slightly solubility method the most thoroughly, in order to evade the indissolubility of rigid molecule chain in most of solvent, adopting that two amido intervals are far away, asymmetrical semi-rigid comonomer, being conducive to above-mentioned improvement.Trace copolymerization does not change the process of liquid crystal behavior and fiber spinning from crystalline state, by destroying the regularity between liquid crystal molecule chain, increases the confusion degree of liquid crystal.The crystallite with certain randomness changes the interaction of fento, and the strength and modulus of fiber is improved.
PPTA fiber spinning from crystalline state liquid is that one presents nematic anisotropic liquid crystalline solution, and it arranges orderly structure by many strands and formed.Be non-correlation when static state between these orderly domain structures, the orientation only in high shear or when extruding stretching between these ordered domains is only relevant.
Containing more polar group in PPTA molecule, large molecule is extended chain conformation, and interaction of molecules power is very strong.Because PPTA fiber is by anisotropic liquid crystal spinning, fiber axial element has high strength and modulus, but because intermolecular force is strong, intermolecular space is less, make its in fiber axis vertical direction compressive strength and fatigue durability poor, and compression after its TENSILE STRENGTH of fiber also have obvious decline.Invention a kind of newly, internal structure vicissitudinous fiber spinning from crystalline state solution.Namely after carrying out micro-copolymerization, change the domain structure dissolving the liquid crystal obtained, main chain introduces flexible structure unit, postpone the generation of phase in version in spinning process of setting, the crystal grain being conducive to making to form microfibrillar structure in spinning process is more tight, improve the degree of orientation of fiber, be conducive to improving the TENSILE STRENGTH in fiber axis vertical direction and fatigue durability.
China Patent No. CN101851809A by comparison we adopt be micro-copolymerization, the content of the comonomer namely added is little, the mol ratio of comonomer and p-phenylenediamine (PPD) is 0-5mol%, and the content of the comonomer that they add is larger, the mol ratio of comonomer and p-phenylenediamine (PPD) is 30-100mol%, the difference of comonomer addition makes the mechanism of comonomer in system change, the comonomer of trace enters the regularity that the later main effect of system is destruction system, and the character of itself is little on system impact, and a large amount of comonomers is not only regularity and is there occurs heavy damage after entering into system, the character of itself also has larger impact to system simultaneously, PPTA resin is originally as the strand that rigidity is stronger, add a large amount of comonomers and then can destroy this system, make to adopt fiber spinning from crystalline state to carry out the preparation of fiber, stoste wet spinning technology can only be adopted.In the processing of aramid fiber, dryly squirt method fiber spinning from crystalline state comparatively wet spinning, have following advantage: (1), from section, wet spinning hollow is many, and demifacet has lousiness; It is dry that to squirt method fiber spinning from crystalline state very tight; 2) contrast wet spinning, solidify in advance in atmosphere and be conducive to carrying out whole macromolecular chain orientation, and then improve the mechanical property of fiber, squirt so dry method fiber spinning from crystalline state have more outstanding compact molecule discharged to.
This patent of China Patent No. CN102070781A have employed four kinds of monomers and carries out combined polymerization, introduce 4,4 '-diaminodiphenyl ether or 4,4 '-diaminodiphenyl sulfide is comonomer, and introducing m-phthaloyl chloride is the 4th monomer, and the shortcoming of this technique is that charging technology is complicated, two kinds of modified monomers added can influence each other, there is competition mechanism, in the specific implementation, be difficult to ensure to obtain that molecular weight is high, the resin solution of even molecular weight distribution.By comparison, we only introduce a kind of comonomer, and whole polymerization process can be fairly simple, and the amount of the monomer introduced in this patent is larger, thus also can the system of PPTA before comparatively serious destruction, therefore hydraulic performance decline can be larger.
China Patent No. CN101851809A adopts dry-spinning process, and previous step gained spinning solution is directly entered hot inert gas path after spinning head, utilizes hot inert gas by the solvent evaporation removing in spinning solution, obtains the precursor solidified.Adopt the fiber solvent of dry production not easily to clean, as a small amount of solvent residual in fruit fiber, in heat treatment process, solvent evaporates or decompose and will make fibres bond, and produce defect, gained fiber embrittlement or lousiness many, intensity is low.
Summary of the invention
The object of this invention is to provide a kind of method improving the Interaction Force of fento in aramid fiber, for the above problem that aramid II fiber exists, by adding micro-comonomer, destroy the regularity of system to a certain extent, formed between fento in dry spray-wet spinning liquid crystal Method spinning process and have interactional fiber, its mechanical property is close with fragrant II fiber, but flexibility and elongation at break all increase.
A kind of method improving the Interaction Force of fento in aramid fiber of the present invention, comprises the following steps:
The synthesis of (a) micro-copolymerization PPTA:
Under nitrogen atmosphere protective condition, first LiCl is dissolved in solvent NMP, then adds micro-comonomer, and add acid absorbent pyridine, stirring makes it dissolve completely, then adds PPD, stirs and makes it dissolve completely, then logical condensation oil bath, under remaining on the temperature conditions of-15 ~-5 DEG C, divide and add TPC three times, stir and make its Homogeneous phase mixing and fully reaction, namely obtain the PPTA resin of modification, its logarithmic viscosity number is 4.0 ~ 6.0dl/g;
Described micro-comonomer is the diamine monomer containing flexible chain structure, for: 3,4 ' diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, 5, (6) diaminourea bisbenzimidazole or 4,4-diaminourea benzyl diethylenediamine.
(b) PPTA-H
2sO
4prepared by liquid crystal solution:
After the PPTA resin drying of described modification, join in the concentrated sulfuric acid, dissolve and obtain PPTA-H
2sO
4liquid crystal solution, the mass percent concentration of PPTA is 18 ~ 20wt%; Through filtration after, vacuum defoamation, after deaeration completes continuation leave standstill 1 ~ 2 hour, to obtain purity spinning solution high as far as possible;
(c) spinning:
PPTA-H after metering
2sO
4liquid crystal solution is extruded from spinnerets, enters air layer and coagulating bath successively;
Spray silk speed is: 10 ~ 40m/min;
Spinning speed is 100 ~ 350m/min;
Air layer height is 6 ~ 15mm;
The H of coagulation bath composition: 0 ~ 10wt%
2sO
4with the H of surplus
2o;
Coagulation bath temperature is 0 ~ 15 DEG C;
(d) washing, neutralization and drying:
The tow that previous step obtained is through washing, and to remove salt on tow and solvent, salt and the solvent of fiber surface absorption can affect the thickness of shaping fiber, crude degree, and then affect the mechanical property of shaping fiber; By sticking to the sulfuric acid of fiber surface in aqua calcis and after coagulating bath; Last 160 ~ 210 DEG C of heating, vacuum dryings, reel reels.
As preferred technical scheme:
A kind of method improving the Interaction Force of fento in aramid fiber as above, the described LiCl concentration be dissolved in solvent NMP is 10 ~ 30g/L, LiCl dissolubility in NMP is good, solubilizing effect is good, consumption is few, easy synthesis heavy polymer, and easily wash away from polymer, fiber colour and the performance of final acquisition are good;
The molar ratio of described micro-comonomer and described p-phenylenediamine (PPD) is 1:99 ~ 5:95;
Molar ratio 1.009 ~ the 1.012:1 of described paraphthaloyl chloride and described micro-comonomer and described p-phenylenediamine (PPD) total amount, considers that paraphthaloyl chloride is easily hydrolyzed, slightly excessive the carrying out being conducive to being polymerized;
The addition of described acid absorbent pyridine is 10 ~ 30ml/L;
After the described PPD of adding, the molar concentration of PPD is 0.2 ~ 0.5mol/L.
A kind of method improving the Interaction Force of fento in aramid fiber as above, described point adds TPC for three times and refers to and add 1/3rd of TPC total amount at every turn, and add for totally three times, the total mol concentration adding rear TPC is 0.2 ~ 0.5mol/L.Point adding TPC for 3 times is performed polymer in order to make diamines first generate certain chain length, and then react with remaining diamines and TPC, the polymer obtained like this, its macromolecular sequential structure there occurs change, corresponding polymer performance also changes, than the disposable better effects if adding TPC.
A kind of method improving the Interaction Force of fento in aramid fiber as above, described solvent NMP first carries out purifying, be specially and NMP is placed in distilling flask, the NMP of purifying is obtained by decompression distillation, main purpose is the moisture contained in desolventizing, then be kept in the container of sealing, and put into molecular sieve drying.
A kind of method improving the Interaction Force of fento in aramid fiber as above, the temperature conditions of described-15 ~-5 DEG C adopts condensation oil bath mode.
A kind of method improving the Interaction Force of fento in aramid fiber as above, described stirring makes its Homogeneous phase mixing and fully reaction refers to that paraphthaloyl chloride just strengthens rotating speed to 500 ~ 3000r/min after all adding at once, remove condensation oil bath after there is pole-climbing, make it continue to react under room temperature state.
A kind of method improving the Interaction Force of fento in aramid fiber as above, further, the PPTA resin of described modification carries out post processing, the PPTA resin of modification is first washed till neutrality with the alkali lye of 0.5 ~ 3mol/L, and then with the washing of a large amount of deionized waters, repeatedly wash and suction filtration, then the resin obtained is put into the baking oven of 60 ~ 120 DEG C, take out after 5 ~ 10h, namely obtain dry micro-copolymerization PPTA resin.
A kind of method improving the Interaction Force of fento in aramid fiber as above, described PPTA-H
2sO
4the shear rate that liquid crystal solution is extruded from spinnerets was with 25000 ~ 5000/ seconds; Described washing refers to the water-bath of fiber by about 20 ~ 30 DEG C, reaches the object removing fiber surface impurity.Described drying refers to 160 ~ 210 DEG C of heating, vacuums dry 2 hours.
A kind of method improving the Interaction Force of fento in aramid fiber as above, the density of described finished fiber is at 1.32 ~ 1.40g/cm
3between, be more or less the same with 1.44 of binary copolymerization, fibrous fracture percentage elongation is 4.2 ~ 8.6%, and fracture strength is between 17.0 ~ 21.8cN/dtex, and initial modulus is between 411 ~ 526cN/dtex., compare with binary copolymerization PPTA fiber, all have and slightly improve, show that this method has certain prospects for commercial application and exploitability.
In the present invention, the chemical constitution of the monomer that synthesis modification PPTA resin is used is as follows:
With 4,4 '-diaminodiphenyl ether (4,4 '-ODA) for example, the chemical reaction occurred in synthetic polymer process in the present invention is as follows:
Beneficial effect:
Present invention achieves the strength and modulus that modified copolyamide fibre maintains PPTA fiber, improve solubility property significantly, improve the flexibility of fiber, fatigue performance, improve and surrender fatigue life, reduce the process costs that PPTA produces.The present invention is easy and simple to handle, and flow process is simple, practical, can heavy industrialization application.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Under nitrogen atmosphere protective condition, the concentration first LiCl of 3g being dissolved in 300mlNMP(LiCl is 10g/L), stir, make after it fully dissolves, add 0.12g3, 4 '-ODA, 3ml acid absorbent pyridine (concentration of pyridine is 10ml/L), be stirred to and fully dissolve and mix, then 6.42g PPD (PPD and 3 is added, the total concentration of 4 '-ODA is 0.2mol/L, PPD and 3, the mol ratio of 4 '-ODA is 99:1), be stirred to and dissolve completely, then the condensation bath of logical-5 DEG C, divide after having friendly relations and add TPC three times, the total concentration at every turn adding 4.06g(TPC is 0.2mol/L), stirring makes it and fully reaction, now strengthening rotating speed is 3000r/min, after there is rod climbing phenomenon, remove condensation oil bath, at room temperature continue reaction, after completion of the reaction, namely the PPTA resin of modification is obtained, its logarithmic viscosity number is 5.32dL/g.After the PPTA resin drying of described modification, join in the concentrated sulfuric acid, dissolve and obtain PPTA-H2SO4 liquid crystal solution, the mass percent concentration of PPTA is 20wt%; After filtering, leave standstill 8 hours, then carry out vacuum defoamation.In advance spinning solution is heated to 70 DEG C, PPTA-H2SO4 liquid crystal solution is extruded from spinnerets after metering, enters air layer and coagulating bath successively, and air layer height is 10mm; The H of coagulation bath composition: 10wt%
2sO
4with the H2O of surplus; Coagulation bath temperature is 4 DEG C; Spray silk speed is 10m/min, and spinning speed is 150m/min.The tow that previous step obtained, through washing, neutralization, 160 DEG C of dryings 2 hours, finally reels on reel.The density of finished fiber is 1.32g/cm3, fracture strength 17.9cN/dtex, elastic modelling quantity 462cN/dtex, elongation at break 5.3%.
Embodiment 2
Under nitrogen atmosphere protective condition, first the LiCl of 9g is dissolved in 300mlNMP (concentration of LiCl is 30g/L), stir, make after it fully dissolves, add 1.5g4, 4 '-ODA, 9ml acid absorbent pyridine (concentration of pyridine is 30ml/L), be stirred to and fully dissolve and mix, then 15.4g PPD (PPD and 4 is added, the total concentration of 4 '-ODA is 0.5mol/L, PPD and 4, the mol ratio of 4 '-ODA is 95:5), be stirred to and dissolve completely, then the condensation bath of logical-5 DEG C, divide after having friendly relations and add TPC three times, the total concentration at every turn adding 10.15g(TPC is 0.5mol/L), stirring makes it and fully reaction, now strengthening rotating speed is 3000r/min, after there is rod climbing phenomenon, remove condensation oil bath, at room temperature continue reaction, after completion of the reaction, namely the PPTA resin of modification is obtained, its logarithmic viscosity number is 5.06dL/g.After the PPTA resin drying of described modification, join in the concentrated sulfuric acid, dissolve and obtain PPTA-H
2sO
4liquid crystal solution, the mass percent concentration of PPTA is 20wt%; Through filtration, vacuum defoamation, in advance spinning solution is heated to 70 DEG C, after metering PPTA-H
2sO
4liquid crystal solution is extruded from spinnerets, enters air layer and coagulating bath successively, and air layer height is 10mm; The H of coagulation bath composition: 10wt%
2sO
4with the H of surplus
2o; Coagulation bath temperature is 4 DEG C; Spray silk speed is 10m/min, and spinning speed is 100m/min.The tow that previous step obtained, through washing, neutralization, 160 DEG C of dryings 2 hours, finally reels on reel.The density of finished fiber is 1.30g/cm
3, fracture strength 17.7cN/dtex, elastic modelling quantity 437cN/dtex, elongation at break 8.5%.
Embodiment 3
Under nitrogen atmosphere protective condition, first the LiCl of 4.8g is dissolved in 300mlNMP (concentration of LiCl is 16g/L), stir, make after it fully dissolves, add 0.40g5, (6) diaminourea bisbenzimidazole, 7.2ml acid absorbent pyridine (concentration of pyridine is 24ml/L), be stirred to and fully dissolve and mix, then 9.53g PPD (PPD and 5 is added, (6) total concentration of diaminourea bisbenzimidazole is 0.3mol/L, PPD and 5, (6) mol ratio of diaminourea bisbenzimidazole is 98:2), be stirred to and dissolve completely, then the condensation bath of logical-5 DEG C, divide after having friendly relations and add TPC three times, the total concentration at every turn adding 6.09g(TPC is 0.3mol/L), stirring makes it and fully reaction, now strengthening rotating speed is 3000r/min, after there is rod climbing phenomenon, remove condensation oil bath, at room temperature continue reaction, after completion of the reaction, namely the PPTA resin of modification is obtained, its logarithmic viscosity number is 6.58dL/g.After the PPTA resin drying of described modification, join in the concentrated sulfuric acid, dissolve and obtain PPTA-H
2sO
4liquid crystal solution, the mass percent concentration of PPTA is 20wt%; Through filtration, vacuum defoamation, in advance spinning solution is heated to 80 DEG C, after metering PPTA-H
2sO
4liquid crystal solution is extruded from spinnerets, enters air layer and coagulating bath successively, and air layer height is 10mm; The H of coagulation bath composition: 10wt%
2sO
4with the H of surplus
2o; Coagulation bath temperature is 4 DEG C; Spray silk speed is 20m/min, and spinning speed is 150m/min.The tow that previous step obtained, through washing, neutralization, 160 DEG C of dryings 2 hours, finally reels on reel.The density of finished fiber is 1.33g/cm
3, fracture strength 18.8cN/dtex, elastic modelling quantity 450cN/dtex, elongation at break 7.7%.
Embodiment 4
Under nitrogen atmosphere protective condition, first the LiCl of 4.8g is dissolved in 300mlNMP (concentration of LiCl is 16g/L), stir, make after it fully dissolves, add 0.36g3, 4 '-ODA, 7.2ml acid absorbent pyridine (concentration of pyridine is 24ml/L), be stirred to and fully dissolve and mix, then 9.53g PPD (PPD and 3 is added, the total concentration of 4 '-ODA is 0.3mol/L, PPD and 3, the mol ratio of 4 '-ODA is 98:2), be stirred to and dissolve completely, then the condensation bath of logical-5 DEG C, divide after having friendly relations and add TPC three times, the total concentration at every turn adding 6.09g(TPC is 0.3mol/L), stirring makes it and fully reaction, now strengthening rotating speed is 3000r/min, after there is rod climbing phenomenon, remove condensation oil bath, at room temperature continue reaction, after completion of the reaction, namely the PPTA resin of modification is obtained, its logarithmic viscosity number is 7.12dL/g.After the PPTA resin drying of described modification, join in the concentrated sulfuric acid, dissolve and obtain PPTA-H
2sO
4liquid crystal solution, the mass percent concentration of PPTA is 20wt%; Through filtration, vacuum defoamation, in advance spinning solution is heated to 70 DEG C, after metering PPTA-H
2sO
4liquid crystal solution is extruded from spinnerets, enters air layer and coagulating bath successively, and air layer height is 10mm; The H of coagulation bath composition: 10wt%
2sO
4with the H of surplus
2o; Coagulation bath temperature is 4 DEG C; Spray silk speed is 30m/min, and spinning speed is 250m/min.The tow that previous step obtained, through washing, neutralization, 160 DEG C of dryings 2 hours, finally reels on reel.The density of finished fiber is 1.36g/cm3, fracture strength 18.3cN/dtex, elastic modelling quantity 468cN/dtex, elongation at break 5.8%.
Embodiment 5
Under nitrogen atmosphere protective condition, first the LiCl of 4.8g is dissolved in 300mlNMP (concentration of LiCl is 16g/L), stir, make after it fully dissolves, add 0.36g4, 4 '-ODA, 7.2ml acid absorbent pyridine (concentration of pyridine is 24ml/L), be stirred to and fully dissolve and mix, then 9.53g PPD (PPD and 4 is added, the total concentration of 4 '-ODA is 0.3mol/L, PPD and 4, the mol ratio of 4 '-ODA is 98:2), be stirred to and dissolve completely, then the condensation bath of logical-5 DEG C, divide after having friendly relations and add TPC three times, the total concentration at every turn adding 6.09g(TPC is 0.3mol/L), stirring makes it and fully reaction, now strengthening rotating speed is 3000r/min, after there is rod climbing phenomenon, remove condensation oil bath, at room temperature continue reaction, after completion of the reaction, namely the PPTA resin of modification is obtained, its logarithmic viscosity number is 8.0dL/g.After the PPTA resin drying of described modification, join in the concentrated sulfuric acid, dissolve and obtain PPTA-H
2sO
4liquid crystal solution, the mass percent concentration of PPTA is 20wt%; Through filtration after, vacuum defoamation, in advance spinning solution is heated to 75 DEG C, after metering PPTA-H
2sO
4liquid crystal solution is extruded from spinnerets, enters air layer and coagulating bath successively, and air layer height is 10mm; The H of coagulation bath composition: 10wt%
2sO
4with the H of surplus
2o; Coagulation bath temperature is 4 DEG C; Spray silk speed is 30m/min, and spinning speed is 250m/min.The tow that previous step obtained, through washing, neutralization, 160 DEG C of dryings 2 hours, finally reels on reel.The density of finished fiber is 1.40g/cm
3, fracture strength 18.8cN/dtex, elastic modelling quantity 476cN/dtex, elongation at break 6.7%.
Embodiment 6
Under nitrogen atmosphere protective condition, first the LiCl of 3g is dissolved in 300mlNMP (concentration of LiCl is 10g/L), stir, make after it fully dissolves, add 0.12g3, 4 '-ODA, 3ml acid absorbent pyridine (concentration of pyridine is 10ml/L), be stirred to and fully dissolve and mix, then 6.42g PPD (PPD and 3 is added, the total concentration of 4 '-ODA is 0.2mol/L, PPD and 3, the mol ratio of 4 '-ODA is 99:1), be stirred to and dissolve completely, then the condensation bath of logical-15 DEG C, divide after having friendly relations and add TPC three times, the total concentration at every turn adding 4.06g(TPC is 0.2mol/L), stirring makes it and fully reaction, now strengthening rotating speed is 3000r/min, after there is rod climbing phenomenon, remove condensation oil bath, at room temperature continue reaction, after completion of the reaction, namely the PPTA resin of modification is obtained, its logarithmic viscosity number is 6.11dL/g.After the PPTA resin drying of described modification, join in the concentrated sulfuric acid, dissolve and obtain PPTA-H
2sO
4liquid crystal solution, the mass percent concentration of PPTA is 20wt%; Through filtration after, vacuum defoamation, in advance spinning solution is heated to 80 DEG C, after metering PPTA-H
2sO
4liquid crystal solution is extruded from spinnerets, enters air layer and coagulating bath successively, and air layer height is 10mm; The H of coagulation bath composition: 10wt%
2sO
4with the H of surplus
2o; Coagulation bath temperature is 4 DEG C; Spray silk speed is 40m/min, and spinning speed is 300m/min.The tow that previous step obtained, through washing, neutralization, 160 DEG C of dryings 2 hours, finally reels on reel.The density of finished fiber is 1.28g/cm
3, fracture strength 20.1cN/dtex, elastic modelling quantity 526cN/dtex, elongation at break 6.2%.
Embodiment 7
Under nitrogen atmosphere protective condition, first the LiCl of 4.8g is dissolved in 300mlNMP (concentration of LiCl is 16g/L), stir, make after it fully dissolves, add 0.36g4, 4 '-ODA, 7.2ml acid absorbent pyridine (concentration of pyridine is 24ml/L), be stirred to and fully dissolve and mix, then 9.53g PPD (PPD and 4 is added, the total concentration of 4 '-ODA is 0.3mol/L, PPD and 4, the mol ratio of 4 '-ODA is 98:2), be stirred to and dissolve completely, then the condensation bath of logical-10 DEG C, divide after having friendly relations and add TPC three times, the total concentration at every turn adding 6.09g(TPC is 0.3mol/L), stirring makes it and fully reaction, now strengthening rotating speed is 3000r/min, after there is rod climbing phenomenon, remove condensation oil bath, at room temperature continue reaction, after completion of the reaction, namely the PPTA resin of modification is obtained, its logarithmic viscosity number is 7.03dL/g.After the PPTA resin drying of described modification, join in the concentrated sulfuric acid, dissolve and obtain PPTA-H
2sO
4liquid crystal solution, the mass percent concentration of PPTA is 20wt%; Through filtration after, vacuum defoamation, in advance spinning solution is heated to 85 DEG C, after metering PPTA-H
2sO
4liquid crystal solution is extruded from spinnerets, enters air layer and coagulating bath successively, and air layer height is 10mm; The H of coagulation bath composition: 10wt%
2sO
4with the H of surplus
2o; Coagulation bath temperature is 4 DEG C; Spray silk speed is 30m/min, and spinning speed is 250m/min.The tow that previous step obtained, through washing, neutralization, 160 DEG C of dryings 2 hours, finally reels on reel.The density of finished fiber is 1.35g/cm
3, intensity 21.8cN/dtex, elastic modelling quantity 492cN/dtex, elongation at break 4.4%.
Claims (6)
1. improve a method for the Interaction Force of fento in aramid fiber, it is characterized in that comprising the following steps:
The synthesis of (a) micro-copolymerization PPTA:
Under nitrogen atmosphere protective condition, first LiCl is dissolved in solvent NMP, then adds micro-comonomer, and add acid absorbent pyridine, stirring makes it dissolve completely, then adds PPD, stirs and makes it dissolve completely, then logical condensation oil bath, under remaining on the temperature conditions of-15 ~-5 DEG C, divide and add TPC three times, stir and make its Homogeneous phase mixing and fully reaction, namely obtain the PPTA resin of modification, its logarithmic viscosity number is between 4.0 ~ 6.0dl/g; Described point adds TPC for three times and refers to and add 1/3rd of TPC total amount at every turn, and add for totally three times, the total mol concentration adding rear TPC is 0.2 ~ 0.5mol/L;
Described micro-comonomer is the diamine monomer containing flexible chain structure, for: 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether or 4,4 '-diaminourea benzyl diethylenediamine;
The molar ratio of described micro-comonomer and described p-phenylenediamine (PPD) is 1:99 ~ 5:95;
(b) PPTA-H
2sO
4prepared by liquid crystal solution:
After the PPTA resin drying of described modification, join in the concentrated sulfuric acid, dissolve and obtain PPTA-H
2sO
4liquid crystal solution, the mass percent concentration of PPTA is 18 ~ 20wt%; After filtering, deaeration prepares spinning solution;
(c) spinning:
In advance spinning solution is heated to 70 ~ 90 DEG C during spinning;
PPTA-H after metering
2sO
4liquid crystal solution is extruded from spinnerets, enters air layer and coagulating bath successively;
Spray silk speed is: 10 ~ 40m/min;
Spinning speed is 100 ~ 350m/min;
Air layer height is 6 ~ 15mm;
The H of coagulation bath composition: 0 ~ 10wt%
2sO
4with the H of surplus
2o;
Coagulation bath temperature is 0 ~ 15 DEG C;
(d) washing, neutralization and drying:
The tow that previous step obtained is through washing, and to remove salt on tow and solvent, by sticking to the sulfuric acid of fiber surface in aqua calcis and after coagulating bath, 160 ~ 210 DEG C of heating, vacuum dryings, finally reel on reel; The density of gained finished fiber is at 1.32 ~ 1.40g/cm
3between, fibrous fracture percentage elongation is 4.2 ~ 8.6%, and fracture strength is between 17.0 ~ 21.8cN/dtex, and initial modulus is between 411 ~ 526cN/dtex.
2. a kind of method improving the Interaction Force of fento in aramid fiber according to claim 1, is characterized in that, the described LiCl concentration be dissolved in solvent NMP is 10 ~ 30g/L;
The molar ratio of described paraphthaloyl chloride and described micro-comonomer and described p-phenylenediamine (PPD) total amount is 1.009 ~ 1.012:1;
The addition of described acid absorbent pyridine is 10 ~ 30ml/L;
After the described PPD of adding, the molar concentration of PPD is 0.2 ~ 0.5mol/L.
3. a kind of method improving the Interaction Force of fento in aramid fiber according to claim 1, it is characterized in that, described solvent NMP first carries out purifying, be specially and NMP is placed in distilling flask, the NMP of purifying is obtained by decompression distillation, main purpose is the moisture contained in desolventizing, is then kept in the container of sealing, and puts into molecular sieve drying.
4. a kind of method improving the Interaction Force of fento in aramid fiber according to claim 1, it is characterized in that, described stirring makes its Homogeneous phase mixing and fully reaction refers to that paraphthaloyl chloride just strengthens rotating speed to 500 ~ 3000r/min after all adding at once, remove condensation oil bath after there is pole-climbing, make it continue to react under room temperature state.
5. a kind of method improving the Interaction Force of fento in aramid fiber according to claim 1, it is characterized in that, further, the PPTA resin of described modification carries out post processing, and the PPTA resin of modification is first washed till neutrality with the alkali lye of 0.5 ~ 3mol/L, and then washs with a large amount of deionized waters, repeatedly washing also suction filtration, then the resin obtained is put into the baking oven of 60 ~ 120 DEG C, take out after 5 ~ 10h, namely obtain dry micro-copolymerization PPTA resin.
6. a kind of method improving the Interaction Force of fento in aramid fiber according to claim 1, is characterized in that, described PPTA-H
2sO
4liquid crystal solution is 2500 ~ 5000/s from the shear rate that spinnerets is extruded; Described washing refers to the water-bath of fiber by 20 ~ 30 DEG C, reaches the object removing salt on tow and solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310419323.XA CN103469343B (en) | 2013-09-13 | 2013-09-13 | A kind of method improving the Interaction Force of fento in aramid fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310419323.XA CN103469343B (en) | 2013-09-13 | 2013-09-13 | A kind of method improving the Interaction Force of fento in aramid fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103469343A CN103469343A (en) | 2013-12-25 |
| CN103469343B true CN103469343B (en) | 2015-10-21 |
Family
ID=49794376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310419323.XA Expired - Fee Related CN103469343B (en) | 2013-09-13 | 2013-09-13 | A kind of method improving the Interaction Force of fento in aramid fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103469343B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107354532A (en) * | 2017-06-28 | 2017-11-17 | 滁州市三和纤维制造有限公司 | A kind of preparation method of polyurethane-modified Fanglun slurry cake |
| CN107652430A (en) * | 2017-09-07 | 2018-02-02 | 烟台泰和新材料股份有限公司 | A kind of production method of the modified p-aramid fiber polymer dope of lithium ion battery plus-negative plate barrier film |
| CN109912832B (en) * | 2017-12-12 | 2022-04-12 | 微宏动力系统（湖州）有限公司 | Aramid fiber slurry, preparation method, aramid fiber diaphragm and lithium battery |
| CN109795840B (en) * | 2017-12-20 | 2020-12-01 | 保定华月胶带有限公司 | Aramid fiber double-layer ring network conveyer belt and preparation method thereof |
| CN111187410B (en) * | 2019-12-27 | 2022-09-09 | 广东优巨先进新材料股份有限公司 | Poly (p-phenylene terephthalamide) liquid crystal polymer and preparation method thereof |
| CN113774509B (en) * | 2021-09-18 | 2022-09-13 | 株洲时代新材料科技股份有限公司 | Method and device for preparing modified meta-aramid fiber through continuous polymerization-dry-wet spinning |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030804A (en) * | 2012-12-31 | 2013-04-10 | 东华大学 | Preparation method of p-phenylene terephthamide resin through low-temperature solution out-phase polycondensation |
-
2013
- 2013-09-13 CN CN201310419323.XA patent/CN103469343B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030804A (en) * | 2012-12-31 | 2013-04-10 | 东华大学 | Preparation method of p-phenylene terephthamide resin through low-temperature solution out-phase polycondensation |
Non-Patent Citations (2)
| Title |
|---|
| 聚对苯二甲酰对苯二胺三元共缩聚改性研究;戴信飞;《中国学位论文全文数据库》;20060116;第15、40、41页 * |
| 聚对苯二甲酰对苯二胺液晶溶液性质及其纤维成形工艺的研究;高向华;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20120215;第42-44页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103469343A (en) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103469343B (en) | A kind of method improving the Interaction Force of fento in aramid fiber | |
| CN101724935B (en) | Polyphenylene terephthalamide fibre and preparation method thereof | |
| CN100549254C (en) | A kind of preparation method of polyacrylonitrile base carbon fiber precursors | |
| CN110344131B (en) | Sericin modified regenerated cellulose fiber and preparation method thereof | |
| CN101195933B (en) | Method for producing Lyocell fibre for tire cord | |
| WO2006128346A1 (en) | Method for preparing regenerated cellulose fibre by two-step coagulating bath process | |
| CN105155033B (en) | A kind of composite fibre of Flameproof polyamide 6 and preparation method thereof | |
| CN101429682A (en) | Method for producing regenerated cellulose fiber by dual-bath coagulation | |
| CN102926022A (en) | Preparation method for aromatic copolyamide fibers | |
| CN1900388A (en) | Anti-wear polyvinyl alcohol aldehyde acetal fiber and its preparing method and use | |
| CN102154727A (en) | High-intensity poly(terephthaloyl-p-phenylene diamine) (PPTA) fiber and preparation method thereof | |
| CN103467736A (en) | Polymerization method capable of effectively controlling phase transformation in PPTA (poly-p-phenylene terephthamide) synthesis process | |
| CN107815741A (en) | A kind of meta-aramid filament preparation process | |
| CN103060940B (en) | A kind of preparation method of medium modulus vinal | |
| CN102383218A (en) | High strength and high modulus para-aramid fiber and preparation method thereof | |
| CN103314035A (en) | Neutralized copolymer crumb and processes for making same | |
| CN102560700B (en) | Para-aramid fine denier fiber and preparation method thereof | |
| JP2016518495A (en) | High-functional polyamide polymer, spinning dope composition containing the same, and molded article thereof | |
| CN1285778C (en) | Method of preparing polyparaphenyl bracing benzdioxazole fibre | |
| CN107629206A (en) | A kind of preparation method of Fanglun l414 fiber | |
| CN102206882B (en) | Method and equipment for continuously manufacturing poly (metaphenylene dimethyl formamide diamino diphenyl sulphone) fibers | |
| CN109705529A (en) | A kind of preparation method based on Fanglun l414 fibrous composite | |
| CN102753589B (en) | Poly-acrylonitrile based polymer solution, manufacturing method thereof, carbon fiber precursor fiber, carbon fiber precursor fiber manufacturing method, and carbon fiber manufacturing method | |
| CN101781813B (en) | Aramid fiber containing fluorine and preparation method thereof | |
| CN104195666B (en) | Method for preparing polyimide fibers based on imidization of o-methyl aryl amide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151021 Termination date: 20180913 |