CN102154726B - Middle modulus poly (p-phenyl-terephthalamide) fiber and preparation method thereof - Google Patents
Middle modulus poly (p-phenyl-terephthalamide) fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a middle modulus poly (p-phenyl-terephthalamide) fiber, which is prepared by the following steps of: adopting a poly (p-phenyl-terephthalamide) polymer with the logarithmic viscosity of 5.5 to8.0dL/g as a raw material, wherein the poly (p-phenyl-terephthalamide) polymer is obtained by a low-temperature solution polycondensation method, and stretching undried wet yarns to preparing the middle modulus poly (p-phenyl-terephthalamide) fiber before washing, neutralizing and drying working procedures of a dry-jet wet spinning process. For the middle modulus poly (p-phenyl-terephthalamide) fiber, the modulus is 550 to 800g/denier and the logarithmic viscosity is 5.0 to 7.5 dL/g. A fiber product obtained by adopting the method not only has gloss of high crystal degree, bright colors, few broken filaments, but also has excellent yarn strength, middle-class modulus and wider application range.
Description
Technical field
The present invention relates to the artificial fibre field; Particularly a kind of PPTA with logarithm viscosity 5.5-8.0dL/g (PPTA) polymer is a raw material; And in dry-jet wet spinning process; Through the stretching to wet yarn, acquisition a kind of is applicable to long yarn intensity that having of industrial scale production is good and Fanglun 1414 of intermediate modulus and preparation method thereof.
Background technology
PPTA (PPTA) fiber adopts the cryogenic fluid polycondensation reaction synthetic in nineteen sixty-five by du pont company, utilizes PPTA/H then
2SO
4Solution has liquid crystal behavior, has invented the method for dry-jet wet-spinning, thereby obtains high-performance Fanglun 1414 (being called for short " aramid fiber II ").The patent of correlation technique is delivered in the U.S. at 1970-1985 successively, for example the patent No.: 3671542,3819587,19730361818,3767756,3869429,3849430,4726922,5001219,5009830,19760720849,19880182826,1980012088,19970950250 etc.
Du pont company carries out the PPTA fiber production since the developing target market of small lot in 1972, and nineteen eighty-two begins to carry out suitability for industrialized production, and name of product is Kevlar.Dutch Akzo dropped into the production of PPTA aramid fiber in 1985, and name of product is Twaron.It is professional that Japan Supreme Being people company merged the Twaron of Dutch Akzo company in 2005, and continue to expand output and compete with E.I.Du Pont Company.Also at test manufacture PPTA and pulp in 1985, this productions stopped in from 1990 to 2000 basically in Korea S Ke Long company, in recovery development in 2006 and found the factory.
Aramid fiber II fiber product has multiple commercial variety, and comprehensive international market commodity can roughly be divided into following several types: 1. general aramid fiber II fiber.Its long yarn intensity is in the 22-23g/d scope, percentage elongation 3.5-3.6%, and the about 550g/d of modulus, this product is used for Application Areass such as tire cord, reinforcing rubber mostly.2. modulus product in the aramid fiber II.Its long yarn intensity is about 23.7g/d, and the about 750g/d of modulus, this product mostly are used for Application Areass such as optical cable reinforcement, unidirectional composite material reinforcement.3. aramid fiber II high modulus product.The about 22-23g/d of its long yarn intensity, modulus 800-950g/d is used for the composite reinforcement mostly.4. also have high strength aramid fiber II fiber product on the market in recent years, the about 26.5-27.5g/d of its long yarn intensity is used for shellproof military use more.In raising variety, some high strength kind restricts export and is supplied to China.
The polymerisation of preparation PPTA is shown below:
The main physical and chemical performance of PPTA comprise strand-NH or-CO end group, molecular weight, molecular weight distribution, density, moisture content, vitrification point, softening temperature, decomposition temperature, inorganic salt content, ash etc., wherein molecular weight and molecular weight distribution having the greatest impact to fibre property.But survey because molecular weight and molecular weight distribution are very difficult; Therefore; Use logarithm viscosity more to help grasping fast the correlation technique information of PPTA and fiber thereof, fully reflect the technological approaches and the technological level of polymerization and spinning as technical indicator.
The molecular weight of directly measuring PPTA is difficulty very, but available its dilution heat of sulfuric acid viscosity is done indication indirectly, general " logarithm viscosity " (the inherent viscosity) that adopt, definition as follows:
η in the formula
InhBe logarithm viscosity, η
RelBe relative viscosity, i.e. the ratio of the viscosity of polymer solution and solvent viscosity, C is the polymer concentration of solution.The mensuration of the logarithm concentration of PPTA is in the 96-98% concentrated acid, and getting C is 0.5g/dL, is to record under 30 ℃ in temperature.The logarithm viscosity number of PPTA alters a great deal in the scope of 1 ~ 10dL/g in the document.
Polymer molecular weight influences the performance of its derivative, and high molecular weight polymers is all adopted in general plastic cement and synthetic fiber industry as far as possible.Make the PPTA fiber too, molecular weight influences the performance of fiber, especially physical property, for example fibre strength and modulus.But the technology of making fiber when molecular weight is too high is very difficult, influences industrial efficiency.
The fusing point of PPTA can not be melt-spun into fiber on its heat decomposition temperature (about 550 ℃).By the technology of generally acknowledging in the industry; PPTA dissolves in the concentrated sulfuric acid; Its concentration can form a liquid crystal aligning property solution (Anisctropic Solution) when 12-19.6%, this solution (also claiming " spinning slurry "); Dry-jet wet-spinning (dry-jet wet spinning) method by generally acknowledging can make high-performance fiber.Dry-jet wet-spinning still belongs to a kind of wet spinning process of synthetic fiber, is characterized in: spinnerets is positioned at the coagulating bath top during spinning, and solidifies the air layer gap that has certain altitude between the liquid level.Spin slurry down,, get into coagulating bath, derive from solidifying pipe through air layer by the spinnerets spray.The slurry silk is solidified the liquid extraction when getting into coagulating bath, precipitate into silk, and most of sulfuric acid diffuses into solidification liquid.Solidify the spun filament that obtains and after technologies such as washing, neutralization, washing, drying, be wound into fiber product.
The applicant is in " a kind of poly P phenylene diamine terephthalamide fiber and preparation method thereof " (application number 200910216761.X) of application on December 14th, 2009, and the modulus that has wherein disclosed this poly P phenylene diamine terephthalamide fiber is the 350-650 gram/dawn.
Summary of the invention
The purpose of this invention is to provide a kind of PPTA with logarithm viscosity 5.5-8.0dL/g (PPTA) polymer is raw material; In dry-jet wet spinning process; Through the stretching to wet yarn, acquisition a kind of is applicable to long yarn intensity that having of industrial scale production is good and Fanglun 1414 of intermediate modulus and preparation method thereof.This poly P phenylene diamine terephthalamide fiber not only has the gloss of Gao Jingdu, lovely luster, and lousiness is few, but also possesses good long yarn intensity and intermediate modulus, and range of application is more extensive.
Concrete technical scheme of the present invention is following:
Modulus PPTA (PPTA) fiber in a kind of; It is characterized in that: PPTA (PPTA) polymer to adopt the logarithm viscosity 5.5-8.0dL/g that the cryogenic fluid polycondensation method obtains is a raw material; And before washing, neutralization and the drying process of dry-jet wet spinning process; Be prepared from through undried wet yarn is still stretched, this Fanglun 1414's modulus is the 550-800 gram/dawn, and logarithm viscosity is 5.0-7.5dL/g.
Modulus Fanglun 1414's preparation method in said; Comprise the synthetic and dry-jet wet-spinning step of PPTA (PPTA) polymer raw material, it is characterized in that: before washing, neutralization and the drying process of dry-jet wet-spinning, undried wet yarn is still carried out stretch processing.
Said wet yarn stretches and is meant: between any two operations before tentatively washing, preliminary neutralization, secondary washing, secondary neutralization, three washings and drying; Perhaps three washing backs with dry before 1 ~ 5 stretched operation that wet yarn is implemented, 0 < total degree of drawing≤3%.
The degree of drawing of said wet yarn can be controlled by the wet speed of yarn in washing, neutralization and drying process, and concrete computational methods are following:
V
2/V
1×V
3/V
2×V
4/V
3×V
5/V
4×V
6/V
5≤1.03
Wherein, V
1Be the wet yarn speed of previous cleaning
V
2Be the wet yarn speed of preliminary neutralization
V
3Be two to wash wet yarn speed
V
4For in the secondary with wet yarn speed
V
5Be the wet yarn speed of three Xian
V
6Be dried yarn speed.
The concrete steps that employing cryogenic fluid polycondensation method according to the invention prepares PPTA (PPTA) polymer are following:
The preparation of A, raw material
P-phenylenediamine (PPD) (p-phenylene diamine) [PPD],
To benzene two tetramethyl acyl chlorides (Terephthaloyl chloride) [TPC],
Helping polysalt is cosolvent: calcium chloride [CaCl
2];
Wherein: the mol ratio of PPD/TPC equals 1.0-1.015, CaCl
2The mol ratio of/PPD equals 1.2-1.7, and the solid content of polyblend is 9-12%;
The polymerization of B, raw material
Nitrogen is fed the agitated reactor after drying, add dry NMP/CaCl then
2Solvent and dry highly purified p-phenylenediamine (PPD) (PPD), rotating mixer is after mixing; Launch the chilled water chuck of agitated reactor; The mixture of p-phenylenediamine (PPD) PPD and solvent NMP is dissolved gradually and in 1 minute to 24 hours, is cooled to 0-20 ℃, add the paraphthaloyl chloride (TPC) of 20-40% wt again, continue to stir temperature control; Through abundant reaction back in 1 minute to 24 hours to 0-20 ℃, the paraphthaloyl chloride TPC of adding surplus in 1 minute to 24 hours again; In this process, the chuck chilled water is changed to 20-40 ℃ of warm water, reaction temperature is increased to 10-20 ℃ gradually, and through after stirring, temperature is gradually steady, rises to 20-50 ℃ naturally; After finishing to reaction, reactant mixture autoreaction still is taken out, uses earlier the NaOH solution neutralization of percentage by weight, spend deionised water 10-40 time again, drying then, the PPTA polymer that can obtain having 5.5-8.0dL/g logarithm viscosity as 10-20%.
Said dry-jet wet spinning process comprise solidify, extraction, spinning, washing, neutralization, drying, oil, operation such as coiling.
Compare with aramid fiber II commercial product, the spinning concrete steps are following:
With above-mentioned logarithm viscosity 5.5-8.0dL/g PPTA (PPTA) polymer; Adding concentration is in the sulfuric acid of 98-100%; Through strong agitation and be warming up to 78-82 ℃, processing concentration is the slurry that spins of 19.0-19.5%, and slurries are sprayed from spinnerets by gear pump metering back after filtering; Spinnerets has more than 100 and spins the hole, and its aperture is 0.05-0.075mm, is the pulping silk after spinning the slurry ejection and spinning the hole; Pass through the 5-10mm air layer, get into the solution face that solidifies, pass through the pipe that solidifies at coagulating basin center then; Outflow below managing; Coagulation bath temperature 0-10 ℃, the acid content of solidification liquid is less than 15%, and coagulating basin solidifies pipe with funnel type or cast; Starch sulfuric acid contained in the silk this moment by the part extraction, become vitriolated wet yarn; Wet yarn continues dirty, in short distance, turns to, and removes most of acid solution; The wet yarn of gained on multistage rotating cylinder roller, carry out the order for the washing of washing/alkali cleaning/washing/alkali cleaning/washing, in and technology; Use drum dryer 120-140 ℃ of drying then; Dried yarn oil the back with the up-coiler rolling on paper web, winding speed is 100 ~ 1000m/min.
Beneficial technical effects of the present invention shows:
1, industrial cost is low, and efficient is high.
In the prior art, it is extremely important to the selection of polymer logarithm viscosity that the high modulus fibre product is made in industrialization.The polymer of employing hyperviscosity carries out slurrying and spinning operation is all very difficult; For example logarithm viscosity is more than 8.0dl/g; Its polymerization time is longer more than 2 times at the normal polymerization time below the 8.0dl/g than logarithm viscosity, and it is all very difficult with spinning operation to join slurry.Because slurry viscosity is high, required stirring and dissolution time are very long when joining slurry; Can be owing to spin slurry pressure superelevation when spinning, cause measuring pump, filament spinning component easily and spin the leakage or the damage of plate; And spinning efficiency is very low, significantly increases running cost, is unwell to suitability for industrialized production.And adopt low viscous polymer, and be that 4.0-5.5dL/g carries out spinning like logarithm viscosity, though easy to operate, the properties of product of gained fiber do not reach requirement, especially intensity and modulus are very low.It is the polymer of 5.5-8.0dl/g that the present invention adopts logarithm viscosity, asks it moderate, avoids polymerization on the one hand, joins the difficulty in slurry and the spinning operation, guarantees that the gained fiber has excellent properties on the one hand, and process efficiency is high, and the industrialization cost is low.
2, the present invention adopts wet yarn is stretched, and local intensity and the modulus that improves the long yarn of fiber is specially adapted to the similar application with other of optical cable reinforcement.Product itself has good performance, has range of application widely, has filled up the market vacancy.
The typical physical performance of this product and similar aramid fiber II product more as shown in table 1:
This product of table 1 compares with the typical physical performance of similar aramid fiber II product
The specific embodiment
Embodiment 1
Adopt like " application number 200910216761.X " said method and make general fiber, the concrete scheme of its polymerization and spinning technique is following:
Said PPTA (PPTA) polymer adopts the cryogenic fluid polycondensation method to carry out the synthetic, specific as follows of raw material:
A, polymer raw comprise:
P-phenylenediamine (PPD) (p-phenylene diamine) [PPD],
To benzene two tetramethyl acyl chlorides (Terephthaloyl chloride) [TPC],
Solvent is (N-methyl pyrrolidone) [NMP],
Helping polysalt (being cosolvent) is calcium chloride (CaCl
2);
Wherein: the mol ratio of PPD/TPC equals 1.0, CaCl
2The mol ratio of/PPD equals 1.4, and the solid content of polyblend is 11%;
B, polymerization:
Nitrogen is fed the agitated reactor after drying, add dry NMP/CaCl then
2Solvent and dry highly purified p-phenylenediamine (PPD) (PPD), rotating mixer is after mixing; Launch the chilled water chuck of agitated reactor; The mixture of p-phenylenediamine (PPD) (PPD) and solvent NMP is dissolved p-phenylenediamine (PPD) (PPD) gradually and in 1 minute, is cooled to 20 ℃, add the paraphthaloyl chloride (TPC) of total amount 30% again, continue to stir cooling; After abundant reaction in 24 hours to 0 ℃, add the paraphthaloyl chloride (TPC) of surplus again; In this process, the chuck chilled water is changed to 30 ℃ of warm water, reaction temperature is increased to 10 ℃ gradually, and through after stirring, temperature is gradually steady, rises to 20 ℃ naturally; After finishing to reaction, reactant mixture autoreaction still is taken out, uses earlier the NaOH solution neutralization of percentage by weight, use 14 grades of washings of deionized water again, drying then, the PPTA polymer that can obtain having 6.5dL/g logarithm viscosity as 10-20%.
C, dry-jet wet-spinning method: comprise solidify, extraction, spinning, washing, neutralization, drying, oil, operation such as coiling.
With above-mentioned logarithm viscosity 6.5dL/g PPTA (PPTA) polymer; Add concentration and be in 99.8% the sulfuric acid; Through strong agitation and be warming up to 81 ℃, process concentration and be 19.35% the slurry that spins, slurries are sprayed from spinnerets by gear pump metering back after filtering; Spinnerets has 1000 to spin the hole, and its aperture is 0.063mm, is the pulping silk after spinning slurry ejection and spinning the hole; Pass through the 7mm air layer, get into the solution face that solidifies, pass through the pipe that solidifies at coagulating basin center then; Outflow below managing; Coagulation bath temperature 0-10 ℃, the acid content 10% of solidification liquid, coagulating basin solidifies pipe with funnel type; Starch sulfuric acid contained in the silk this moment by the part extraction, become vitriolated wet yarn; Wet yarn continues dirty, in short distance, turns to, and removes most of acid solution; The wet yarn of gained on multistage rotating cylinder, carry out order for the washing of washing/alkali cleaning/washing/alkali cleaning/washing, in and technology, use drum dryer 135 ℃ of dryings then, dried yarn oils afterwards with the up-coiler rolling on paper web, winding speed is 300m/min.
The long yarn performance of gained is listed in the table 2.
Table 2 is implemented the mechanical property of the fiber of wet yarn stretching before drying
Embodiment 2
The polymerization of this example is consistent with embodiment 1 described technology with spinning technique, stretches but in spinning process, carried out wet yarn before the drying.
In the present embodiment, mainly before drying process, carried out wet yarn and stretched, promptly through adjustment V
6/ V
5Ratio is realized stretching.Through different V
6/ V
5Ratio, the gained fibre property is as shown in table 3.
Table 3 is through the dry preceding mechanical property of implementing the wet little stretch processing fiber of yarn
Above data spell out intensity and the modulus of when washing and drying, making the wet yarn stretching can increasing of substep fiber.
Claims (4)
1. modulus Fanglun 1414's preparation method in a kind; Synthetic and the dry-jet wet-spinning step that comprises the PPTA polymer raw material; It is characterized in that: the PPTA polymer to adopt the logarithm viscosity 5.5-8.0dL/g that the cryogenic fluid polycondensation method obtains is a raw material; And before washing, neutralization and the drying process of dry-jet wet spinning process; Be prepared from through undried wet yarn is still stretched, this Fanglun 1414's modulus is the 550-800 gram/dawn, and logarithm viscosity is 5.0-7.5dL/g;
Said wet yarn stretches and is meant: between any two operations before tentatively washing, preliminary neutralization, secondary washing, secondary neutralization, three washings and drying; Perhaps three washing backs with dry before 1 ~ 5 stretched operation that wet yarn is implemented, 0 < total degree of drawing≤3%;
The degree of drawing of said wet yarn is controlled by the wet speed of yarn in washing, neutralization and drying process, and concrete computational methods are following:
V
2/V
1×V
3/V
2×V
4/V
3×V
5/V
4×V
6/V
5≤1.03
Wherein, V
1Be the wet yarn speed of preliminary washing
V
2Be the wet yarn speed of preliminary neutralization
V
3Be the wet yarn speed of secondary washing
V
4For in the secondary with wet yarn speed
V
5Be three wet yarn speed of Xian Di
V
6Be dried yarn speed.
According to claim 1 in modulus Fanglun 1414's preparation method, it is characterized in that: the synthetic employing cryogenic fluid polycondensation method of said PPTA polymer raw material, concrete steps are following:
The preparation of A, raw material
P-phenylenediamine (PPD) (p-phenylene diamine) [PPD],
Paraphthaloyl chloride (Terephthaloyl chloride) [TPC],
Helping polysalt is cosolvent: calcium chloride [CaCl
2];
Wherein: the mol ratio of PPD/TPC equals 1.0-1.015, CaCl
2The mol ratio of/PPD equals 1.2-1.7, and the solid content of polyblend is 9-12%;
The polymerization of B, raw material
Nitrogen is fed the agitated reactor after drying, add dry NMP/CaCl then
2Solvent and dry highly purified p-phenylenediamine (PPD), rotating mixer is after mixing; Launch the chilled water chuck of agitated reactor; The mixture of p-phenylenediamine (PPD) PPD and solvent NMP is dissolved gradually and in 1 minute to 24 hours, is cooled to 0-20 ℃, add the paraphthaloyl chloride of 20-40 wt% again, continue to stir temperature control; Through abundant reaction back in 1 minute to 24 hours to 0-20 ℃, the paraphthaloyl chloride of adding surplus in 1 minute to 24 hours again; In this process, the chuck chilled water is changed to 20-40 ℃ of warm water, reaction temperature is increased to 10-20 ℃ gradually, and through after stirring, temperature is gradually steady, rises to 20-50 ℃ naturally; After finishing to reaction, reactant mixture autoreaction still is taken out, uses earlier the NaOH solution neutralization of percentage by weight, spend deionised water 10-40 time again, drying then, the PPTA polymer that can obtain having 5.5-8.0dL/g logarithm viscosity as 10-20%.
According to claim 1 in modulus Fanglun 1414's preparation method, it is characterized in that: said dry-jet wet spinning process comprises and solidifies, extraction, spinning, washing, neutralization, drying, oils and reel operation.
4. like the said middle modulus Fanglun 1414's of claim 3 preparation method, it is characterized in that: the spinning concrete steps are following:
With above-mentioned logarithm viscosity 5.5-8.0dL/g PPTA polymer; Adding concentration is in the sulfuric acid of 98-100%; Through strong agitation and be warming up to 78-82 ℃, processing concentration is the slurry that spins of 19.0-19.5%, and slurries are sprayed from spinnerets by gear pump metering back after filtering; Spinnerets has more than 100 and spins the hole, and its aperture is 0.05-0.075mm, is the pulping silk after spinning the slurry ejection and spinning the hole; Pass through the 5-10mm air layer, get into the solution face that solidifies, pass through the pipe that solidifies at coagulating basin center then; Outflow below managing; Coagulation bath temperature 0-10 ℃, the acid content of solidification liquid is less than 15%, and coagulating basin solidifies pipe with funnel type or cast; Starch sulfuric acid contained in the silk this moment by the part extraction, become vitriolated wet yarn; Wet yarn continues dirty, in short distance, turns to, and removes most of acid solution; The wet yarn of gained on multistage rotating cylinder roller, carry out the order for the washing of washing/alkali cleaning/washing/alkali cleaning/washing, in and technology; Use drum dryer 120-140 ℃ of drying then; Dried yarn oil the back with the up-coiler rolling on paper web, winding speed is 100-1000m/min.
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| CN102797061B (en) * | 2012-08-15 | 2015-01-07 | 中蓝晨光化工研究设计院有限公司 | Multistage stretching technology for manufacture aramid fiber III |
| CN103726124B (en) * | 2014-01-03 | 2018-04-27 | 烟台泰和新材料股份有限公司 | A kind of preparation method of original liquid coloring p-aramid fiber long filament and products thereof |
| CN106757451B (en) * | 2016-12-15 | 2019-06-04 | 江苏宝德新材料有限公司 | A method of producing the poly- 1,3,4- oxadiazoles long filament of aromatic series |
| CN110029405A (en) * | 2019-04-08 | 2019-07-19 | 东华大学 | A kind of preparation method of high uniformity p-aramid fiber |
| CN112458583B (en) * | 2020-10-22 | 2021-09-17 | 烟台泰和新材料股份有限公司 | Para-aramid fiber, preparation method thereof and application of para-aramid fiber in preparation of molten metal splash protection clothing |
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