CN102732991B - Dyeable aromatic polyamide mixed fiber and preparation method thereof - Google Patents
Dyeable aromatic polyamide mixed fiber and preparation method thereof Download PDFInfo
- Publication number
- CN102732991B CN102732991B CN201210227835.1A CN201210227835A CN102732991B CN 102732991 B CN102732991 B CN 102732991B CN 201210227835 A CN201210227835 A CN 201210227835A CN 102732991 B CN102732991 B CN 102732991B
- Authority
- CN
- China
- Prior art keywords
- aromatic polyamide
- spinning
- solvent
- chloride
- polymer
- 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.)
- Active
Links
Landscapes
- Artificial Filaments (AREA)
Abstract
The invention discloses a method for preparing optical anisotropic aromatic polyamide mixed spinning slurry by uniformly mixing high-crystallinity para-aromatic polyamide polymers and non-crystalline polymers under a molecular state, a dyeable aromatic polyamide mixed fiber prepared by the spinning slurry, and a dyeing method of the aromatic polyamide mixed fiber, wherein the dyeable aromatic polyamide mixed fiber is prepared by polymerizing 2, 5-diamino Y group benzene, paraphthaloyl chloride and polrvinyl chloride in a solvent system, preparing spinning slurry, filtering the slurry, spinning by dry-jet wet spinning, drying and rolling. The aromatic polyamide mixed fiber provided by the invention has the advantages of excellent dyeing property, high color fastness and bright colors; physical properties such as fatigue durability, corrosion resistance and adhesiveness of rubbers also are increased significantly, so that application prospect is wider.
Description
Technical field
The present invention relates to a kind of macromolecule synthesising technology field, especially a kind of aromatic polyamide blended fiber and preparation method thereof that dyes.
Background technology
Aramid fiber, aromatic polyamide fibre can be divided into p-aramid fiber (PPTA) and meta-aramid (poly(isophthaloyl metaphenylene diamine)), the structure manufacture that wherein p-aramid fiber is connected by amide groups (CONH) linearity by phenyl ring.It is well feature that p-aramid fiber has high strength, high-modulus, heat resistance, chemical resistance, low-shrinkage and fatigue resistance.Therefore, be widely used in the new technologies and methods fields such as national defence, Aero-Space, auto industry, composite enhancing, sports equipment, High temperature textiles.P-aramid fiber (PPTA) adopts Low-temperature Solution Polycondensation reaction synthetic in nineteen sixty-five Dupont (Dupont) the Stephanie Kwolek of research institute and Herbert Blades, then through PPTA/H
2sO
4solution is made liquid crystal aligning spinning slurry, utilizes the dry method that squirts to carry out spinning, thereby obtains p-aramid fiber.But the problems such as the compression strength that p-aramid fiber is lower and higher vitrification point, up to 270 ℃, dye difficult, and adherence is low.Many Application Areass require the high-quality color and luster of fiber, and therefore, the dyeing of aramid fiber has very important significance.
In order to solve the above problems, people have carried out a large amount of research work, correlation technique is patent US5,073,440 and US5,135,687 proposition PPTA and water soluble polymer PVP (PVP) are dissolved to mix to manufacture and are had the physical property that keeps p-aramid fiber in the concentrated sulfuric acid solvent of being fuming, improve dyeability, adherence, hydrophilic technology.But the people such as Simonutti in 2002 manufacture PPTA/PVP mixed solution with the concentrated sulfuric acid of being fuming, utilize solid-state cross polarization evil spirit angle rotation
13c nuclear magnetic resoance spectrum detects compatibility, and result shows that mixed solution is not that molecular state is evenly miscible, the nano complex that Er Shuo nanometer unit is separated (Nanocomposite) form.Above-mentioned technology points out that high crystalline macromolecule PPTA and amorphism Macromolecule PVP are not that molecular state is evenly miscible, the nano complex that Er Shuo nanometer unit is separated, the more problems such as inhomogeneous mixing causes the inhomogeneities of composite fibre, and while eventually there is dyeing equalization is inconsistent.
Summary of the invention
The object of the present invention is to provide a kind of high crystalline contraposition aromatic polyamide polymer and amorphism macromolecule miscible uniformly under molecular state, hold optics anisotropy (Anisotropy) the aromatic polyamide blended fiber and preparation method thereof that can dye, blended fiber of the present invention has good dyeability, COLOR FASTNESS is high, bright-colored, and fatigue durability, the physical properties such as adherence corrosion-resistant and rubber are also significantly improved.
Object of the present invention realizes by following technical proposals: a kind of aromatic polyamide blended fiber (YPPTA/PVC) that dyes, it is characterized in that: by 2, 5-diaminourea Y base benzene (YPPD) and paraphthaloyl chloride (TPC) the in molar ratio proportioning of 1:1 join in solvent, quantity of solvent separately be take and is guaranteed that aromatic polyamide polymerization original content in solution liquid is as the criterion as 10～18wt% (percentage by weight), add polyvinyl chloride (PVC), the amount of PVC is 2～20wt% of aromatic polyamide polymer weight, through low temperature polymerization, prepare spinning slurry, slurries filter, dry-jet wet spinning, dry, winding process is prepared from.
Described solvent is wherein a kind of or their mixture of N-methyl pyrrolidone (NMP), dimethylacetylamide (DMAc), dimethyl formamide (DMF), and the moisture of solvent is 20ppm～70ppm.
Can the dye production method of high strength aromatic polyamide blended fiber of the present invention follows these steps to carry out:
A, low temperature polymerization:
Polymerization single polymerization monomer 2, 5-diaminourea Y base benzene and paraphthaloyl chloride reaction with same mole, nitrogen is passed into the reactor after oven dry, 2, 5-diaminourea Y base benzene and polyvinyl chloride (PVC), add in the solvent that contains villaumite, evenly fully stir, polymerization temperature is 0 ~ 5 ℃, paraphthaloyl chloride is reinforced at twice, add for the first time 65% of total amount, continue fully to stir 0 ~ 5 ℃ of cooling, moment adds 35% of total amount more for the second time, rapid stirring, reaction is through " pole-climbing ", " gel ", after " blending " three phases, stop, total reaction time 20 ~ 30 minutes, obtain polymer (YPPTA).
B, prepare spinning slurry:
The hydrogen chloride producing in above-mentioned polymerisation (HCl), adopt inorganic salts and oxide to neutralize, in the YPPTA of granular, add the inorganic salts of the hydrogen chloride equimolar amounts producing in polymerisation or stir uniformly with oxide, whipping temp is 40 ~ 60 ℃, fully stir and within 3 hours, stop afterwards mixing, prepare evenly miscible spinning slurry of high crystalline macromolecule aromatic polyamide polymer and amorphism macromolecule PVC.
C, spinning:
Above-mentioned spinning slurry is filtered above through 200 orders, after filtration, by pump, from spinnerets, sprayed, be pulping silk, through 5～15mm air layer, enter 0～5 ℃ and solidify liquid level (solidification liquid is comprised of water and polymer solvent, in solidification liquid, solvent is 15～25wt%), become solvent-laden wet yarn, after removing water, tow adopts the mode of hot-rolling contact drying and forced air drying use to be dried, 180～260 ℃ of baking temperatures, the speed of coiling is 300～500m/min.
In the present invention, the compound structure of polymer spun silk stock solution monomer used is as follows:
In 2,5-diaminourea Y base benzene, Y is CN, NO
2among a kind of.
Described villaumite adopts calcium chloride (CaCl
2), lithium chloride (LiCl), potassium chloride (KCl) is a kind of or their mixture wherein.Chloride content in polymer solvent system is 0 ~ 8wt%, and chloride content surpasses the above the effect also degree of polymerization not being risen of 8wt%, especially considers that cost angle increases inorganic salts consumption nonsensical.
Described inorganic salts and oxide are calcium carbonate (CaCO
3), lithium carbonate (Li
2cO
3), calcium oxide (CaO), lithia (Li
2o) a kind of or their mixture wherein.
The molecular weight 60 of described polyvinyl chloride (PVC), 000 ~ 80,000, it is 2 ~ 20wt% of aromatic polyamide polymer weight that polyvinyl chloride (PVC) adds optimised quantity, the consumption of polyvinyl chloride (PVC) surpasses 20wt% and causes above falling low molecular crystalline orientation (Orientation) effect, reduces fibre strength; Consumption is less than 2wt% and causes below COLOR FASTNESS not ideal enough.
Described spinnerets aperture arranges in rows, and the position in the aperture in every row is skew than adjacent row's aperture, and meristogenetic the one-tenths silk layer evenly separating is provided.Lines of orifices is 8 to 12 rows preferably, aperture centre-to-centre spacing 0.8 ~ 2.0mm, and in a row, the centre-to-centre spacing between adjacent aperture is identical with the centre distance between the aperture of adjoining in row.
The useful technique effect that the present invention brings is as follows:
One, the present invention by modified monomer provide a kind of high crystalline contraposition aromatic polyamide polymer (YPPTA) and amorphism macromolecule (PVC) miscible uniformly under molecular state, prepare and hold optics anisotropy (Anisotropy) aromatic polyamide blend spinning slurries, utilize blend spinning slurries can directly carry out spinning, the process procedure of greatly simplifying obtains blended fiber.
Two, blended fiber provided by the invention dyes by ACID DYES or cation dyes, make the aramid fiber of dyeing, COLOR FASTNESS is high, bright-colored, and improve fatigue durability, the physical property such as corrosion-resistant, there is range of application widely, especially filled up the market vacancy that requires high strength, multicoloured clothing industry.Fine through actual tests product Color of the present invention, refer to table one.
The specific embodiment
Below by the embodiment description concrete to the present invention; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
1, low temperature polymerization:
Nitrogen is passed into the reactor after oven dry, to build under nitrogen environment, press TPC:CyPPD=equimolar ratio, first by high-purity (more than 99.9%) 2, 5-diaminobenzene formonitrile HCN (CyPPD) 8.442kg and polyvinyl chloride (PVC) 3.338kg add in 100 liters of dimethylacetylamides (DMAc) solvent, then after stirring is dissolved CyPPD completely, in the cooling 10min of freezing chuck of use reactor, be cooled to 0 ~ 5 ℃, add paraphthaloyl chloride (TPC) 8.366kg to continue to stir fully and be cooled to again 0 ~ 5 ℃ after reaction 20min, moment adds paraphthaloyl chloride (TPC) 4.505kg again, rapid stirring, there is pole-climbing in reaction system, gel, after being blended again, reaction stops, obtain the inherent viscosity 5.5dL/g of polymer (CyPPTA),
Wherein: paraphthaloyl chloride (TPC) feeds in raw material as carrying out at twice, add for the first time 65% of total amount, for the second time 35% of reinforced total amount, aromatic polyamide polymer (CyPPTA) content in polymeric solution is 15wt%, polyvinyl chloride (PVC) amount is the 20wt% of aromatic polyamide polymer weight, and the moisture of solvent is 50ppm.
2, prepare spinning slurry:
In above-mentioned polymerisation, produce hydrogen chloride (HCl), adopt inorganic salts or and oxide come in and hydrogen chloride (HCl), to blending the inner inorganic salts that add of polymer (CyPPTA), stir uniformly, addition is 4.78kg, reaction temperature is 40 ~ 50 ℃, fully reacts and within 3 hours, stops reaction afterwards.
Wherein: the present embodiment inorganic salts are lithium carbonate (Li
2cO
3), the inorganic salts amount adding equals hydrogen chloride (HCl) molal quantity generating;
3, spinning:
Above-mentioned spinning slurry has gear pump metering to spray from spinnerets after filtering; Spinnerets has 1000 hole counts, and its aperture is 0.07mm, and aperture and hole are long than 1.5, squeezing out spinneret orifice is pulping silk, through 6mm air layer, enter and solidify liquid level, enter 0 ~ 5 ℃ and solidify liquid level (solidification liquid is comprised of water and polymer solvent, in solidification liquid, solvent is 15 ~ 25wt%), become solvent-laden wet yarn, after removing water, tow adopts hot-rolling contact drying and forced air drying and is dried by mode, 260 ℃ of baking temperatures, the speed of coiling is 350m/min.
The high strength aromatic polyamide blended fiber (CyPPTA/PVC) that the present embodiment obtains, the polymer of inherent viscosity 5.5dL/g of take is prepared from as starting point, its inherent viscosity is less than 0.5dL/g compared with the inherent viscosity fall of polymer, the specific targets of this fiber comprise: TENSILE STRENGTH 20g/d, initial modulus 500g/d, elongation at break 3.5%, filament number 1.5D, bundle yarn fiber number 1500D.
Embodiment 2:
1, low temperature polymerization:
Nitrogen is passed into the reactor after oven dry, to build under nitrogen environment, press TPC:CyPPD=equimolar ratio, first by high-purity (more than 99.9%) 2, 5-diaminobenzene formonitrile HCN (CyPPD) 8.442kg and polyvinyl chloride (PVC) 0.835kg add in 100 liters of dimethylacetylamides (DMAc) solvent, then after stirring is dissolved CyPPD completely, in the cooling 10min of freezing chuck of use reactor, be cooled to 0 ~ 5 ℃, add paraphthaloyl chloride (TPC) 8.366kg to continue to stir fully and be cooled to again 0 ~ 5 ℃ after reaction 20min, moment adds paraphthaloyl chloride (TPC) 4.505kg again, rapid stirring, there is pole-climbing in reaction system, gel, after being blended again, reaction stops, obtain the inherent viscosity 6.5dL/g of polymer (CyPPTA),
Wherein: paraphthaloyl chloride (TPC) feeds in raw material as carrying out at twice, add for the first time 65% of total amount, for the second time 35% of reinforced total amount, aromatic polyamide polymer (CyPPTA) content in polymeric solution is 15wt%, polyvinyl chloride (PVC) amount is the 5wt% of aromatic polyamide polymer weight, and the moisture of solvent is 50ppm.
2, prepare spinning slurry:
In above-mentioned polymerisation, produce hydrogen chloride (HCl), adopt inorganic salts or and oxide come in and hydrogen chloride (HCl), to blending the inner inorganic salts that add of polymer (CyPPTA), stir uniformly, addition is 4.78kg, reaction temperature is 40 ~ 50 ℃, fully reacts and within 3 hours, stops reaction afterwards.
Wherein: the present embodiment inorganic salts are lithium carbonate (Li
2cO
3), the inorganic salts amount adding equals hydrogen chloride (HCl) molal quantity generating;
3, spinning:
Above-mentioned spinning slurry has gear pump metering to spray from spinnerets after filtering; Spinnerets has 1000 hole counts, and its aperture is 0.07mm, and aperture and hole are long than 1.5, squeezing out spinneret orifice is pulping silk, through 6mm air layer, enter and solidify liquid level, enter 0 ~ 5 ℃ and solidify liquid level (solidification liquid is comprised of water and polymer solvent, in solidification liquid, solvent is 15 ~ 25wt%), become solvent-laden wet yarn, after removing water, tow adopts hot-rolling contact drying and forced air drying and is dried by mode, 260 ℃ of baking temperatures, the speed of coiling is 350m/min.
A kind of high strength aromatic polyamide blended fiber (CyPPTA/PVC) that the present embodiment obtains, the polymer of inherent viscosity 6.5dL/g of take is prepared from as starting point, its inherent viscosity is less than 0.5dL/g compared with the inherent viscosity fall of polymer, the specific targets of this fiber comprise: TENSILE STRENGTH 23g/d, initial modulus 600g/d, elongation at break 3.2%, filament number 1.5D, bundle yarn fiber number 1500D.
Embodiment 3:
1, low temperature polymerization:
Nitrogen is passed into the reactor after oven dry, to build under nitrogen environment, press TPC:CyPPD=equimolar ratio, first by high-purity (more than 99.9%) 2, 5-diaminobenzene formonitrile HCN (CyPPD) 8.442kg and polyvinyl chloride (PVC) 0.334kg add in 100 liters of dimethylacetylamides (DMAc) solvent, then after stirring is dissolved CyPPD completely, in the cooling 10min of freezing chuck of use reactor, be cooled to 0 ~ 5 ℃, add paraphthaloyl chloride (TPC) 8.366kg to continue to stir fully and be cooled to again 0 ~ 5 ℃ after reaction 20min, moment adds paraphthaloyl chloride (TPC) 4.505kg again, rapid stirring, there is pole-climbing in reaction system, gel, after being blended again, reaction stops, obtain the inherent viscosity 7.0dL/g of polymer (CyPPTA),
Wherein: paraphthaloyl chloride (TPC) feeds in raw material as carrying out at twice, add for the first time 65% of total amount, for the second time 35% of reinforced total amount, aromatic polyamide polymer (CyPPTA) content in polymeric solution is 15wt%, polyvinyl chloride (PVC) amount is the 2wt% of aromatic polyamide polymer weight, and the moisture of solvent is 50ppm.
2, prepare spinning slurry:
In above-mentioned polymerisation, produce hydrogen chloride (HCl), adopt inorganic salts or and oxide come in and hydrogen chloride (HCl), to blending the inner inorganic salts that add of polymer (CyPPTA), stir uniformly, addition is 4.78kg, reaction temperature is 40 ~ 50 ℃, fully reacts and within 3 hours, stops reaction afterwards.
Wherein: the present embodiment inorganic salts are lithium carbonate (Li
2cO
3), the inorganic salts amount adding equals hydrogen chloride (HCl) molal quantity generating;
3, spinning:
Above-mentioned spinning slurry has gear pump metering to spray from spinnerets after filtering; Spinnerets has 1000 hole counts, and its aperture is 0.07mm, and aperture and hole are long than 1.5, squeezing out spinneret orifice is pulping silk, through 6mm air layer, enter and solidify liquid level, enter 0 ~ 5 ℃ and solidify liquid level (solidification liquid is comprised of water and polymer solvent, in solidification liquid, solvent is 15 ~ 25wt%), become solvent-laden wet yarn, after removing water, tow adopts hot-rolling contact drying and forced air drying and is dried by mode, 260 ℃ of baking temperatures, the speed of coiling is 350m/min.
The high strength aromatic polyamide blended fiber (CyPPTA/PVC) that the present embodiment obtains, the polymer of inherent viscosity 7.0dL/g of take is prepared from as starting point, its inherent viscosity is less than 0.5dL/g compared with the inherent viscosity fall of polymer, the specific targets of this fiber comprise: TENSILE STRENGTH 24g/d, initial modulus 650g/d, elongation at break 3.0%, filament number 1.5D, bundle yarn fiber number 1500D.
Embodiment 4:
1, low temperature polymerization:
Nitrogen is passed into the reactor after oven dry, to build under nitrogen environment, press TPC:CyPPD=equimolar ratio, first high-purity (more than 99.9%) 2,5-diaminobenzene formonitrile HCN (CyPPD) 5.433kg and polyvinyl chloride (PVC) 0.537kg are added to 100 liters of dimethylacetylamides (DMAc)/7.493kgCaCl
2in dicyandiamide solution, then after stirring is dissolved CyPPD completely, in the cooling 10min of freezing chuck of use reactor, be cooled to 0 ~ 5 ℃, add paraphthaloyl chloride (TPC) 5.384kg to continue to stir fully reaction 20min and be cooled to 0 ~ 5 ℃ afterwards again, moment adds paraphthaloyl chloride (TPC) 2.899kg again, rapid stirring, there is pole-climbing in reaction system, gel, after being blended again, reaction stops, and obtains the inherent viscosity 6.0dL/g of polymer (CyPPTA);
Wherein: paraphthaloyl chloride (TPC) feeds in raw material as carrying out at twice, add for the first time 65% of total amount, for the second time 35% of reinforced total amount, aromatic polyamide polymer (CyPPTA) content in polymeric solution is 10wt%, polyvinyl chloride (PVC) amount is the 5wt% of aromatic polyamide polymer weight, the moisture of solvent is 20ppm, the CaCl in polymer solvent system
2content is 8wt%.
2, prepare spinning slurry:
In above-mentioned polymerisation, produce hydrogen chloride (HCl), adopt inorganic salts or and oxide come in and hydrogen chloride (HCl), to blending the inner inorganic salts that add of polymer (CyPPTA), stir uniformly, addition is 3.076kg, reaction temperature is 40 ~ 50 ℃, fully reacts and within 3 hours, stops reaction afterwards.
Wherein: the present embodiment inorganic salts are lithium carbonate (Li
2cO
3), the inorganic salts amount adding equals hydrogen chloride (HCl) molal quantity generating;
3, spinning:
Above-mentioned spinning slurry has gear pump metering to spray from spinnerets after filtering; Spinnerets has 1000 hole counts, and its aperture is 0.07mm, and aperture and hole are long than 1.5, squeezing out spinneret orifice is pulping silk, through 6mm air layer, enter and solidify liquid level, enter 0 ~ 5 ℃ and solidify liquid level (solidification liquid is comprised of water and polymer solvent, in solidification liquid, solvent is 15 ~ 25wt%), become solvent-laden wet yarn, after removing water, tow adopts hot-rolling contact drying and forced air drying and is dried by mode, 260 ℃ of baking temperatures, the speed of coiling is 350m/min.
A kind of high strength aromatic polyamide blended fiber (CyPPTA/PVC) that the present embodiment obtains, the polymer of inherent viscosity 6.0dL/g of take is prepared from as starting point, its inherent viscosity is less than 0.5dL/g compared with the inherent viscosity fall of polymer, the specific targets of this fiber comprise: TENSILE STRENGTH 22g/d, initial modulus 550g/d, elongation at break 3.0%, filament number 1.5D, bundle yarn fiber number 1500D.
Embodiment 5:
1, low temperature polymerization:
Nitrogen is passed into the reactor after oven dry, to build under nitrogen environment, press TPC:CyPPD=equimolar ratio, first high-purity (more than 99.9%) 2,5-diaminobenzene formonitrile HCN (CyPPD) 11.078kg and polyvinyl chloride (PVC) 1.095kg are added to 100 liters of dimethylacetylamides (DMAc)/4.685kgCaCl
2in dicyandiamide solution, then after stirring is dissolved CyPPD completely, in the cooling 10min of freezing chuck of use reactor, be cooled to 0 ~ 5 ℃, add paraphthaloyl chloride (TPC) 10.979kg to continue to stir fully reaction 20min and be cooled to 0 ~ 5 ℃ afterwards again, moment adds paraphthaloyl chloride (TPC) 5.912kg again, rapid stirring, there is pole-climbing in reaction system, gel, after being blended again, reaction stops, and obtains the inherent viscosity 5.2dL/g of polymer (CyPPTA);
Wherein: paraphthaloyl chloride (TPC) feeds in raw material as carrying out at twice, add for the first time 65% of total amount, for the second time 35% of reinforced total amount, aromatic polyamide polymer (CyPPTA) content in polymeric solution is 18wt%, polyvinyl chloride (PVC) amount is the 5wt% of aromatic polyamide polymer weight, the moisture of solvent is 70ppm, the CaCl in polymer solvent system
2content is 5wt%.
2, prepare spinning slurry:
In above-mentioned polymerisation, produce hydrogen chloride (HCl), adopt inorganic salts or and oxide come in and hydrogen chloride (HCl), to blending the inner inorganic salts that add of polymer (CyPPTA), stir uniformly, addition is 6.273kg, reaction temperature is 40 ~ 50 ℃, fully reacts and within 3 hours, stops reaction afterwards.
Wherein: the present embodiment inorganic salts are lithium carbonate (Li
2cO
3), the inorganic salts amount adding equals hydrogen chloride (HCl) molal quantity generating;
3, spinning:
Above-mentioned spinning slurry has gear pump metering to spray from spinnerets after filtering; Spinnerets has 1000 hole counts, and its aperture is 0.07mm, and aperture and hole are long than 1.5, squeezing out spinneret orifice is pulping silk, through 6mm air layer, enter and solidify liquid level, enter 0 ~ 5 ℃ and solidify liquid level (solidification liquid is comprised of water and polymer solvent, in solidification liquid, solvent is 15 ~ 25wt%), become solvent-laden wet yarn, after removing water, tow adopts hot-rolling contact drying and forced air drying and is dried by mode, 260 ℃ of baking temperatures, the speed of coiling is 350m/min.
A kind of high strength aromatic polyamide blended fiber (CyPPTA/PVC) that the present embodiment obtains, the polymer of inherent viscosity 5.2dL/g of take is prepared from as starting point, its inherent viscosity is less than 0.5dL/g compared with the inherent viscosity fall of polymer, the specific targets of this fiber comprise: TENSILE STRENGTH 21g/d, initial modulus 530g/d, elongation at break 3.3%, filament number 1.5D, bundle yarn fiber number 1500D.
Embodiment 6:
1, low temperature polymerization:
Nitrogen is passed into the reactor after oven dry, to build under nitrogen environment, press TPC:NPPD=equimolar ratio, first by high-purity (more than 99.9%) 2-nitro-1, 4-this diamines (NPPD) 6.126kg and polyvinyl chloride (PVC) 0.567kg add in 100 liters of 1-METHYLPYRROLIDONEs (NMP)/4.685kgKCl dicyandiamide solution, then after stirring is dissolved CyPPD completely, in the cooling 10min of freezing chuck of use reactor, be cooled to 0 ~ 5 ℃, add paraphthaloyl chloride (TPC) 5.276kg to continue to stir fully and be cooled to again 0 ~ 5 ℃ after reaction 20min, moment adds paraphthaloyl chloride (TPC) 2.845kg again, rapid stirring, there is pole-climbing in reaction system, gel, after being blended again, reaction stops, obtain the inherent viscosity 4.8dL/g of polymer (NPPTA),
Wherein: paraphthaloyl chloride (TPC) feeds in raw material as carrying out at twice, add for the first time 65% of total amount, for the second time 35% of reinforced total amount, aromatic polyamide polymer (NPPTA) content in polymeric solution is 10wt%, polyvinyl chloride (PVC) amount is the 5wt% of aromatic polyamide polymer weight, the moisture of solvent is 50ppm, and the KCl content in polymer solvent system is 5wt%.
2, prepare spinning slurry:
In above-mentioned polymerisation, produce hydrogen chloride (HCl), adopt inorganic salts or and oxide come in and hydrogen chloride (HCl), to blending the inner inorganic salts that add of polymer (NPPTA), stir uniformly, addition is 4.082kg, reaction temperature is 40 ~ 50 ℃, fully reacts and within 3 hours, stops reaction afterwards.
Wherein: the present embodiment inorganic salts are calcium carbonate (CaCO
3), the inorganic salts amount adding equals hydrogen chloride (HCl) molal quantity generating;
3, spinning:
Above-mentioned spinning slurry has gear pump metering to spray from spinnerets after filtering; Spinnerets has 1000 hole counts, and its aperture is 0.07mm, and aperture and hole are long than 1.5, squeezing out spinneret orifice is pulping silk, through 6mm air layer, enter and solidify liquid level, enter 0 ~ 5 ℃ and solidify liquid level (solidification liquid is comprised of water and polymer solvent, in solidification liquid, solvent is 15 ~ 25wt%), become solvent-laden wet yarn, after removing water, tow adopts hot-rolling contact drying and forced air drying and is dried by mode, 260 ℃ of baking temperatures, the speed of coiling is 350m/min.
A kind of high strength aromatic polyamide blended fiber (NPPTA/PVC) that the present embodiment obtains, the polymer of inherent viscosity 4.8dL/g of take is prepared from as starting point, its inherent viscosity is less than 0.5dL/g compared with the inherent viscosity fall of polymer, the specific targets of this fiber comprise: TENSILE STRENGTH 20g/d, initial modulus 500g/d, elongation at break 3.3%, filament number 1.5D, bundle yarn fiber number 1500D.
Embodiment 7:
1, low temperature polymerization:
Nitrogen is passed into the reactor after oven dry, to build under nitrogen environment, press TPC:NPPD=equimolar ratio, first by high-purity (more than 99.9%) 2-nitro-1, this diamines of 4-(NPPD) 4.594kg and polyvinyl chloride (PVC) 0.425kg add in 100 liters of dimethyl formamides (DMF) solvent, then after stirring is dissolved CyPPD completely, in the cooling 10min of freezing chuck of use reactor, be cooled to 0 ~ 5 ℃, add paraphthaloyl chloride (TPC) 3.959kg to continue to stir fully and be cooled to again 0 ~ 5 ℃ after reaction 20min, moment adds paraphthaloyl chloride (TPC) 2.131kg again, rapid stirring, there is pole-climbing in reaction system, gel, after being blended again, reaction stops, obtain the inherent viscosity 4.5dL/g of polymer (NPPTA),
Wherein: paraphthaloyl chloride (TPC) feeds in raw material as carrying out at twice, add for the first time 65% of total amount, for the second time 35% of reinforced total amount, aromatic polyamide polymer (NPPTA) content in polymeric solution is 10wt%, polyvinyl chloride (PVC) amount is the 5wt% of aromatic polyamide polymer weight, and the moisture of solvent is 50ppm.
2, prepare spinning slurry:
In above-mentioned polymerisation, produce hydrogen chloride (HCl), adopt inorganic salts or and oxide come in and hydrogen chloride (HCl), to blending the inner inorganic salts that add of polymer (NPPTA), stir uniformly, addition is 0.896kg, reaction temperature is 40 ~ 50 ℃, fully reacts and within 3 hours, stops reaction afterwards.
Wherein: the present embodiment inorganic salts are lithia (Li
2o), the inorganic salts amount adding equals hydrogen chloride (HCl) molal quantity generating;
3, spinning:
Above-mentioned spinning slurry has gear pump metering to spray from spinnerets after filtering; Spinnerets has 1000 hole counts, and its aperture is 0.07mm, and aperture and hole are long than 1.5, squeezing out spinneret orifice is pulping silk, through 6mm air layer, enter and solidify liquid level, enter 0 ~ 5 ℃ and solidify liquid level (solidification liquid is comprised of water and polymer solvent, in solidification liquid, solvent is 15 ~ 25wt%), become solvent-laden wet yarn, after removing water, tow adopts hot-rolling contact drying and forced air drying and is dried by mode, 260 ℃ of baking temperatures, the speed of coiling is 350m/min.
A kind of high strength aromatic polyamide blended fiber (NPPTA/PVC) that the present embodiment obtains, the polymer of inherent viscosity 4.5dL/g of take is prepared from as starting point, its inherent viscosity is less than 0.5dL/g compared with the inherent viscosity fall of polymer, the specific targets of this fiber comprise: TENSILE STRENGTH 18g/d, initial modulus 480g/d, elongation at break 3.3%, filament number 1.5D, bundle yarn fiber number 1500D.
Claims (2)
1. the aromatic polyamide blended fiber that can dye, is characterized in that: by 2,5-diaminourea Y base benzene and paraphthaloyl chloride in molar ratio the proportioning of 1:1 join in solvent, said Y base is CN or NO
2quantity of solvent separately be take and is guaranteed that aromatic polyamide polymerization original content in solution liquid is as the criterion as 10～18wt%, add polyvinyl chloride, the amount of PVC is 2～20wt% of aromatic polyamide polymer weight, through low temperature polymerization, prepare spinning slurry, slurries filtration, dry-jet wet spinning, dry, winding process is prepared from.
2. the aromatic polyamide blended fiber that can a dye preparation method, is characterized in that: follow these steps to carry out
A, low temperature polymerization:
Polymerization single polymerization monomer 2,5-diaminourea Y base benzene and paraphthaloyl chloride reaction with same mole, said Y base is CN or NO
2, nitrogen is passed into the reactor after oven dry, 2,5-diaminourea Y base benzene and polyvinyl chloride, add in the solvent that contains villaumite, evenly fully stirs, polymerization temperature is 0 ~ 5 ℃, and paraphthaloyl chloride is reinforced at twice, adds for the first time 65% of total amount, continue fully to stir 0 ~ 5 ℃ of cooling, moment adds 35% of total amount, rapid stirring more for the second time, reaction is through stopping after " pole-climbing ", " gel ", " blending " three phases, total reaction time 20 ~ 30 minutes, obtains polymer
B, prepare spinning slurry:
The hydrogen chloride producing in above-mentioned polymerisation, adopt inorganic salts and oxide to neutralize, in the YPPTA of granular, add inorganic salts or the oxide of the hydrogen chloride equimolar amounts producing in polymerisation to stir uniformly, said YPPTA is contraposition aromatic polyamide polymer, whipping temp is 40 ~ 60 ℃, fully stir and within 3 hours, stop afterwards mixing, prepare evenly miscible spinning slurry of high crystalline macromolecule aromatic polyamide polymer and amorphism macromolecule PVC
C, spinning:
Above-mentioned spinning slurry is filtered above through 200 orders, after filtration, by pump, from spinnerets, sprayed, it is pulping silk, through 5～15mm air layer, enter 0～5 ℃ and solidify liquid level, become solvent-laden wet yarn, after removing water, tow adopts the mode of hot-rolling contact drying and forced air drying use to be dried, 180～260 ℃ of baking temperatures, and the speed of coiling is 300～500m/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210227835.1A CN102732991B (en) | 2012-07-04 | 2012-07-04 | Dyeable aromatic polyamide mixed fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210227835.1A CN102732991B (en) | 2012-07-04 | 2012-07-04 | Dyeable aromatic polyamide mixed fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102732991A CN102732991A (en) | 2012-10-17 |
| CN102732991B true CN102732991B (en) | 2014-05-07 |
Family
ID=46989266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210227835.1A Active CN102732991B (en) | 2012-07-04 | 2012-07-04 | Dyeable aromatic polyamide mixed fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102732991B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383218A (en) * | 2011-08-26 | 2012-03-21 | 南充易安新材料有限公司 | High strength and high modulus para-aramid fiber and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269879A (en) * | 1995-03-29 | 1996-10-15 | Ykk Kk | Production of polyamide dyed product |
-
2012
- 2012-07-04 CN CN201210227835.1A patent/CN102732991B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383218A (en) * | 2011-08-26 | 2012-03-21 | 南充易安新材料有限公司 | High strength and high modulus para-aramid fiber and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JP特开平8-269879A 1996.10.15 |
| PVC/PA共混改性研究进展;李飞等;《聚氯乙烯》;20110131;第39卷(第1期);第1-3页第2-3节 * |
| 李飞等.PVC/PA共混改性研究进展.《聚氯乙烯》.2011,第39卷(第1期),第1-3页第2-3节. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102732991A (en) | 2012-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101921395B (en) | High-performance heterocyclic aramid fiber as well as preparation and application thereof | |
| CN102383218B (en) | High strength and high modulus para-aramid fiber and preparation method thereof | |
| CN109930230A (en) | A kind of copolyamide industrial yarn and preparation method thereof | |
| JP6629296B2 (en) | High strength copolymerized aramid fiber and method for producing the same | |
| CN101724935A (en) | Polyphenylene terephthalamide fibre and preparation method thereof | |
| EP2048268B1 (en) | Process for producing an aromatic copolyamide fiber | |
| CN103409854A (en) | Production method of carbon fiber | |
| US10233288B2 (en) | Highly functional polyamide polymer, spinning dope composition containing same, and molded product thereof | |
| CN102154727A (en) | High-intensity poly(terephthaloyl-p-phenylene diamine) (PPTA) fiber and preparation method thereof | |
| CN112695390A (en) | High-elongation low-modulus para-aramid fiber and preparation method thereof | |
| CN103469343B (en) | A kind of method improving the Interaction Force of fento in aramid fiber | |
| CN112375216A (en) | High molecular weight para-aramid pulp and preparation method thereof | |
| CN102677225B (en) | Aromatic polyamide/aromatic polyimide blended fiber and preparation method thereof | |
| CN107675283B (en) | High-strength aromatic copolyamide fiber and preparation method thereof | |
| CN103408749A (en) | Chinlon 6 section for bromochlorodifluoromethane (BCF) carpet yarn and preparation method thereof | |
| CN109402764B (en) | High-strength low-elongation polyamide 6 staple fiber and preparation method thereof | |
| CN102154726B (en) | Middle modulus poly (p-phenyl-terephthalamide) fiber and preparation method thereof | |
| CN116623309B (en) | Polymer coloring method, spinning color paste, spinning solution and colored fiber | |
| CN102732991B (en) | Dyeable aromatic polyamide mixed fiber and preparation method thereof | |
| CN103628172B (en) | A kind of preparation method of ternary copolyimide fiber | |
| CN113668091B (en) | High-strength high-elongation heterocyclic aromatic polyamide fiber and preparation process thereof | |
| CN101781813B (en) | Aramid fiber containing fluorine and preparation method thereof | |
| CN107151833B (en) | A kind of polyimide fine denier fiber and preparation method thereof | |
| CN104372435A (en) | Aromatic polysulfone amide copolymer fiber containing PPTA (Poly-p-phenylene Terephthalamide) chain section and manufacturing method thereof | |
| CN114574990B (en) | Preparation method of easy-to-dye and easy-to-shape spandex fiber |
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 |