CN117661140A - Spinning sizing agent for high-strength creep-resistant and antistatic nylon 66 fiber and preparation method thereof - Google Patents
Spinning sizing agent for high-strength creep-resistant and antistatic nylon 66 fiber and preparation method thereof Download PDFInfo
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- 229920002302 Nylon 6,6 Polymers 0.000 title claims abstract description 143
- 238000009987 spinning Methods 0.000 title claims abstract description 99
- 239000000835 fiber Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 title abstract description 5
- 238000004513 sizing Methods 0.000 title abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 56
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 56
- 239000002002 slurry Substances 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012621 metal-organic framework Substances 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 17
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011268 mixed slurry Substances 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000009736 wetting Methods 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 7
- 229920000767 polyaniline Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- FPSZFXFLOLSRSJ-UHFFFAOYSA-N ClC(Cl)(Cl)C=C[SiH3] Chemical compound ClC(Cl)(Cl)C=C[SiH3] FPSZFXFLOLSRSJ-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 2
- 239000013255 MILs Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- CDQVJNJTOFLAKD-UHFFFAOYSA-N [SiH4].ClC=C(Cl)Cl Chemical compound [SiH4].ClC=C(Cl)Cl CDQVJNJTOFLAKD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 238000004132 cross linking Methods 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 238000011049 filling Methods 0.000 abstract description 4
- 238000010309 melting process Methods 0.000 abstract description 2
- 238000002296 dynamic light scattering Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 13
- 238000009826 distribution Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000013207 UiO-66 Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VJWGHGJYLCJIEK-UHFFFAOYSA-N 1,4-bis(6-methylheptoxy)-1,4-dioxobutane-2-sulfonic acid Chemical compound CC(C)CCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCC(C)C VJWGHGJYLCJIEK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a spinning sizing agent for high-strength creep-resistant and antistatic nylon 66 fiber and a preparation method thereof, wherein in the method, a physical filling mode is adopted, and a metal oxide and an MOF are used for filling and modifying PA66, namely, in the melting process of PA66, the metal oxide, the MOF and the PA66 form a physical crosslinking point, the intermolecular acting force is enhanced, the doped particles can form the physical crosslinking point between molecules, the intermolecular acting force is enhanced, the intermolecular steric hindrance is effectively increased, the sliding of molecular chains is prevented, and the creep-resistant effect is generated; in addition, after doping the modified spinning slurry, the conductivity of the PA66 fiber can be greatly improved, and the antistatic capacity of the fiber is enhanced. The PA66 fiber obtained by the method has the advantages of strong creep resistance and excellent antistatic performance under the double-effect synergistic effect of metal oxide and MOF.
Description
Technical Field
The invention relates to the technical field of melt spinning, in particular to spinning sizing agent for high-strength creep-resistant and antistatic nylon 66 fibers and a preparation method thereof.
Background
Since 1935 w.h.carothers invented nylon 66 (PA 66), the dupont company in 1939 established a nylon 66 production plant with a world production of 4000 tons in the first year. Along with the gradual deepening of people on the understanding of nylon 66, the nylon 66 with high molecular weight and high viscosity is developed, equipment related to the preparation of the nylon 66 is gradually perfected, the performance improvement on the nylon 66 is gradually enhanced, the existing nylon 66 has high mechanical strength, good toughness, excellent heat resistance, wear resistance, corrosion resistance and other performances, and under matched equipment and technology, the nylon 66 with excellent performance can be prepared by industrialized production, and the mass production of the high-performance nylon 66 is widely applied to the civil field and the military field.
The PA66 fiber is prepared by performing polycondensation reaction on ethylenediamine containing 6 carbon atoms and adipic acid containing 6 carbon atoms to obtain polyamide resin, and performing melt spinning to obtain polyamide fiber; the PA66 fiber molecular chain has high order and arrangement regularity, excellent molecular chain orientation and crystallinity, and has intermolecular forces such as hydrogen bond and Van der Waals force, so that the PA66 fiber molecular chain has excellent mechanical properties and better rigidity and strength, but because the PA66 molecular chain structure is regular, branched chains and hetero chains are fewer, intermolecular forces are fewer, the molecular chain is easy to slip, the fiber is irreversibly changed in the use process, so that the PA66 fiber has poor shape retention in the use process, is easy to deform to generate irreversible deformation to cause creep, has poor antistatic property, and is easy to generate static electricity in the use process to destroy the original use comfort of the fiber.
Therefore, the spinning slurry for the nylon 66 fiber with high creep resistance and antistatic performance and the preparation process thereof have important significance to the industry.
Disclosure of Invention
In view of the above, the invention provides a spinning slurry for high-strength creep-resistant and antistatic nylon 66 fiber and a preparation method thereof, wherein in the spinning slurry, a physical filling mode is adopted, and a metal oxide and an MOF are used for filling and modifying PA66, namely, in the melting process of PA66, the metal oxide and the MOF form a physical crosslinking point with PA66, the intermolecular acting force is enhanced, the doped particles can form a physical crosslinking point between molecules, the intermolecular acting force is enhanced, the intermolecular steric hindrance is effectively increased, the sliding of molecular chains is prevented, and the creep-resistant effect is generated; in addition, after doping the modified spinning slurry, the conductivity of the PA66 fiber can be greatly improved, and the antistatic capacity of the fiber is enhanced. The PA66 fiber obtained by the method has the advantages of strong creep resistance and excellent antistatic performance under the double-effect synergistic effect of metal oxide and MOF.
The technical scheme of the invention is as follows:
the spinning slurry for the high-strength creep-resistant and antistatic nylon 66 fiber comprises the following components in parts by weight:
94-100 parts of PA66 powder, 1-5 parts of metal oxide, 0.5-1 part of Metal Organic Framework (MOF), 0.1-0.5 part of coupling agent, 0.1-0.5 part of surfactant, 0.1-0.5 part of wetting dispersant and 0.2-0.5 part of electrolyte.
Preferably, the PA66 powder has an average particle size of5 μm and a bulk density of 0.5g/cm 3 A melting point of 265 ℃; the powdery PA66 raw material can improve the spinnability of spinning slurry and improve the surface morphology and mechanical properties of fibers.
Preferably, the metal oxide is one or more of nano iron oxide, nano copper oxide and nano aluminum oxide, and the average particle size of the metal oxide is 300nm; the metals in the metal oxide have conductivity and low cost, and can realize the antistatic purpose at low cost.
Preferably, the MOF is one or more of MOF-UiO-66 (Zr), HKUST-1, ZIF-8 and MILs, and the average particle size of the MOF is 200nm; the excellent specific surface area and porous structure of MOF and its special microscopic surface effect promote the expression of intermolecular forces of fiber molecular chains, so that the conductivity and creep resistance of the product can be improved when the MOF is added into PA66 fiber.
Preferably, the coupling agent is a silane coupling agent; the silane coupling agent is one or more of trichloroethylene silane, triethoxyvinyl silane, gamma-aminopropyl triethoxysilane and trichloropropenyl silane; the silane coupling agent is a mature product in the market, the material is easy to obtain, the cost is low, the crosslinking and adhesion of the PA66 powder, the metal oxide and the MOF can be promoted by adding the coupling agent, and the uniformity and spinnability of the spinning slurry are improved.
Preferably, the surfactant is anionic surfactant, and is one or more of alkylbenzene sulfonate, polysiloxane, fatty alcohol polyoxyethylene ether phosphate and polyoxyethylene monolaurate.
Preferably, the wetting dispersant is diisooctyl sodium sulfosuccinate, the solid content is 70-75%, the pH is 5.0-7.0, and the viscosity is less than 200.
The addition of the surfactant and the wetting dispersant can enhance the dispersion uniformity of the spinning slurry, improve the compatibility among the components, promote the adhesion and crosslinking among the components and enhance the spinnability of the final spinning slurry.
Preferably, the electrolyte comprises polyaniline (PAn) and lithium chloride (LiCl), and the mass ratio of polyaniline (PAn) to lithium chloride (LiCl) is 1:1.
The preparation method of the spinning slurry comprises the following steps:
(1) Preparing materials: weighing for standby according to the proportion of each component in the spinning slurry;
(2) Preparation of a metal oxide system:
adding metal oxide and electrolyte into a beaker, adding a certain amount of deionized water, and stirring for 2-3h at room temperature to obtain mixed slurry A; grinding the mixed slurry A in a ball mill for 3-4h to ensure that the average particle size of particles in the mixed slurry A is less than 150nm, and obtaining mixed slurry B with uniform dispersion; filtering the mixed slurry B, and drying a filter cake to remove water to obtain a uniformly dispersed metal oxide system for later use;
the process can obtain a uniformly dispersed metal oxide system, and the particle size of the metal oxide is reduced through ball milling treatment, so that a foundation is created for uniform mixing in the subsequent PA66 spinning slurry preparation;
(3) Preparing MOF material:
adding MOF, wetting dispersant and surfactant into a beaker, stirring at room temperature for 2-3h to obtain a mixture A, then putting the mixture A into a ball mill for ball milling for 3-4h, and stopping milling when the average particle size of the MOF in the mixture A is smaller than 100nm to obtain a mixture B; filtering the mixture B which is qualified in grinding and uniformly dispersed, filtering and drying to obtain MOF material, and bagging for later use;
after being mixed with a wetting dispersant and a surfactant and ball-milled, the MOF can obtain a mixed system with good compatibility and adhesion, and the mixed system is mixed with a metal oxide system to prepare PA66 fibers with excellent creep resistance and antistatic property;
(4) Preparing a PA66 spinning slurry dispersion system:
adding PA66 powder, a surfactant and a coupling agent into a stirring barrel, stirring at 300-500rpm for 30-50min, then adding the metal oxide system in the step (2) and the MOF material in the step (3), and continuously stirring at 400-700rpm for 2-3h to obtain uniformly mixed PA66 spinning slurry; in order to ensure spinnability of the spinning dope, the dispersibility of the particles (particle size and particle size distribution) in the spinning dope was measured using a dynamic light scattering analyzer (DLS).
The dispersion uniformity of the spinning dope and the compatibility between the components are main factors for ensuring the performance of the dope; the raw materials of the spinning slurry are formed and arranged, so that the compatibility of the raw materials is good; the preparation method of the spinning slurry enables the raw materials to be uniformly dispersed, so that the spinning fiber with high creep resistance and high antistatic performance can be prepared by using the spinning slurry.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the modified PA66 spinning slurry fiber has the advantages of simple operation and excellent spinnability; the addition of metal oxide and MOF in the melt spinning slurry can enable PA66 molecular chains to form a plurality of physical crosslinking points in the pre-spinning process to form a three-dimensional communication structure, promote the molecular chain arrangement and improve the orientation degree of the PA66 molecular chains; the orientation degree and the crystallinity of the PA66 molecular chain are improved, and the PA66 molecular chain can be prevented from sliding and moving when the PA66 molecular chain is acted by external force, so that the prepared PA66 fiber has good creep resistance mechanical property.
2. In the invention, the PA66 fiber added with the metal oxide and the MOF has larger specific surface area and porosity, a three-dimensional crosslinked conductive communication network is formed, and the electrolyte is distributed in the three-dimensional crosslinked conductive communication network to enhance the conductive performance of the fiber, thereby achieving the antistatic effect; in addition, the synergistic action force of the metal oxide and the MOF induces the establishment of a three-dimensional intercommunicating conductive network between the PA66 fibers, thereby increasing the final conductive capacity of the material and achieving the antistatic effect
3. In the process of spinning the PA66 fiber, the temperature of eight heating areas of a double-screw extruder is set to enable PA66 molecular chains to be entangled and opened to generate orientation rearrangement, and the rotating speed of the double screws is set to provide shearing force for spinning sizing agent to enable PA66 molecular chains to be crystallized; in the post spinning, the melt spinning-super stretching method is adopted, so that the orientation degree and the crystallinity of the PA66 molecular chain can be improved more possibly, and a three-dimensional crosslinked conductive network is effectively constructed; the arrangement ensures that all components in the spinning slurry are fully combined to obtain the PA66 fiber with good creep resistance and static resistance.
4. The PA66 fiber prepared by the invention has excellent creep resistance mechanical property and antistatic property, and can be applied to the fields of civil textiles, national defense and military industry and aerospace to play a vital role.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
In the following examples and comparative examples of the present invention, the PA66 powder was in a state after grinding by a grinderThe average particle size is 5 μm and the bulk density is 0.5g/cm 3 A melting point of 265 ℃; the electrolyte consists of PAn and LiCl, and the mass ratio of PAn to LiCl is 1:1.
Example 1
A preparation method of spinning slurry comprises the following steps:
(1) Preparation of a metal oxide system:
50g of nano ferric oxide and 2g of electrolyte are mixed and added into a beaker, deionized water is added, and stirring is carried out for 2.5 hours at room temperature, thus obtaining mixed slurry A; grinding the mixed slurry A in a ball mill for 3 hours to ensure that the average particle size of particles in the mixed slurry A is less than 150nm, and obtaining uniformly dispersed mixed slurry B; filtering and drying the mixed slurry B to remove water to obtain a uniformly dispersed metal oxide system for standby;
(2) Preparing MOF material:
respectively adding 5g of MOF-UiO-66 (Zr), 1g of diisooctyl sulfosuccinate sodium and 1g of alkylbenzene sulfonate into a beaker, stirring at room temperature for 2.5 hours to obtain a mixture A, then placing the mixture A into a ball mill for grinding treatment for 3.5 hours, and stopping grinding when the average particle size of MOF in the mixture A is smaller than 100nm to obtain a mixture B; filtering and drying the mixture B which is qualified in grinding and uniformly dispersed to obtain MOF material, and bagging for later use;
(3) Preparing a PA66 spinning slurry dispersion system:
adding 470g of PA66 powder, 2.5g of alkylbenzene sulfonate and 2g of silane coupling agent into a stirring barrel, stirring at 450rpm for 45min, then adding 25g of metal oxide system in the step (1) and 5g of MOF material in the step (2), and continuously stirring at 600rpm for 3h to prepare uniformly mixed PA66 spinning slurry;
to ensure spinnability of the spin dope, the dispersibility of the particles (particle size and particle size distribution) in the spin dope was measured using a dynamic light scattering analyzer (DLS), as shown in table 2.
The PA66 spin dope prepared in this example is designated PA66-1.
Comparative example 1
Comparative example 1 differs from example 1 in that no metal oxide and MOF were added to the PA66 spinning dope.
The PA66 spin dope prepared above was designated PA66-1.1.
Example 2
A preparation method of spinning slurry comprises the following steps:
(1) Preparation of a metal oxide system:
as in example 1.
(2) Preparing MOF material:
as in example 1.
(3) Preparing a PA66 spinning slurry dispersion system:
the well-mixed PA66 spinning dope was prepared by adding 490g of the PA66 powder, 2.5g of the alkylbenzene sulfonate and 2g of the silane coupling agent to a stirring vessel, stirring at 450rpm for 45min, then adding 5g of the metal oxide system of step (1) and 5g of the MOF material of step (2) and continuing stirring at 600rpm for 3 h.
To ensure spinnability of the spinning dope, the dispersibility of the particles (particle size and particle size distribution) in the spinning dope was measured using a dynamic light scattering analyzer (DLS), and the results are shown in table 2.
The PA66 spin dope prepared in this example is designated PA66-2.
Example 3
A preparation method of spinning slurry comprises the following steps:
(1) Preparation of a metal oxide system:
as in example 1.
(2) Preparing a PA66 spinning slurry dispersion system:
adding 475g of PA66 powder, 2.5g of alkylbenzene sulfonate and 2g of silane coupling agent into a stirring barrel, stirring at 450rpm for 45min, then adding 25g of the metal oxide system in the step (1), and continuously stirring at 600rpm for 3h to prepare uniformly mixed PA66 spinning slurry;
to ensure spinnability of the spinning dope, the dispersibility of the particles (particle size and particle size distribution) in the spinning dope was measured using a dynamic light scattering analyzer (DLS), and the results are shown in table 2.
The PA66 spin dope prepared in this example is designated PA66-3.
Example 4
A preparation method of spinning slurry comprises the following steps:
(1) Preparation of a metal oxide system:
as in example 1.
(2) Preparing a PA66 spinning slurry dispersion system:
adding 4815 g of PA66 powder, 2.5g of alkylbenzene sulfonate and 2g of silane coupling agent into a stirring barrel, stirring at 450rpm for 45min, and then adding 15g of the metal oxide system in the step (1) and continuously stirring at 600rpm for 3h to prepare uniformly mixed PA66 spinning slurry;
to ensure spinnability of the spinning dope, the dispersibility of the particles (particle size and particle size distribution) in the spinning dope was measured using a dynamic light scattering analyzer (DLS), and the results are shown in table 2.
The PA66 spin dope prepared in this example is designated PA66-4.
Example 5
A preparation method of spinning slurry comprises the following steps:
(1) Preparation of a metal oxide system:
as in example 1.
(2) Preparing a PA66 spinning slurry dispersion system:
adding 495g of PA66 powder, 2.5g of alkylbenzene sulfonate and 2g of silane coupling agent into a stirring barrel, stirring at 450rpm for 45min, and then adding 5g of the metal oxide system in the step (1) and continuously stirring at 600rpm for 3h to prepare uniformly mixed PA66 spinning slurry;
to ensure spinnability of the spinning dope, the dispersibility of the particles (particle size and particle size distribution) in the spinning dope was measured using a dynamic light scattering analyzer (DLS), and the results are shown in table 2.
The PA66 spin dope prepared in this example was designated PA66-5.
Example 6
A preparation method of spinning slurry comprises the following steps:
(1) Preparing MOF material:
as in example 1.
(2) Preparing a PA66 spinning slurry dispersion system:
adding 495g of PA66 powder, 2.5g of alkylbenzene sulfonate and 2g of silane coupling agent into a stirring barrel, stirring at 450rpm for 45min, and then adding 5g of MOF material prepared in the step (1) and continuously stirring at 600rpm for 3h to prepare uniformly mixed PA66 spinning slurry;
to ensure spinnability of the spinning dope, the dispersibility of the particles (particle size and particle size distribution) in the spinning dope was measured using a dynamic light scattering analyzer (DLS), and the results are shown in table 2.
The PA66 spin dope prepared in this example is designated PA66-6.
Example 7
A preparation method of spinning slurry comprises the following steps:
(1) Preparing MOF material:
as in example 1.
(2) Preparing a PA66 spinning slurry dispersion system:
adding 4966 g of PA66 powder, 2.5g of alkylbenzene sulfonate and 2g of silane coupling agent into a stirring barrel, stirring at 450rpm for 45min, and then adding 4g of MOF material prepared in the step (1) and continuously stirring at 600rpm for 3h to prepare uniformly mixed PA66 spinning slurry;
to ensure spinnability of the spinning dope, the dispersibility of the particles (particle size and particle size distribution) in the spinning dope was measured using a dynamic light scattering analyzer (DLS), and the results are shown in table 2.
The PA66 spin dope prepared in this example is designated PA66-7.
Example 8
A preparation method of spinning slurry comprises the following steps:
(1) Preparing MOF material:
as in example 1.
(2) Preparing a PA66 spinning slurry dispersion system:
adding 497g of PA66 powder, 2.5g of alkylbenzene sulfonate and 2g of silane coupling agent into a stirring barrel, stirring at 450rpm for 45min, and then adding 3g of MOF material prepared in the step (1) and continuously stirring at 600rpm for 3h to prepare uniformly mixed PA66 spinning slurry;
to ensure spinnability of the spinning dope, the dispersibility of the particles (particle size and particle size distribution) in the spinning dope was measured using a dynamic light scattering analyzer (DLS), and the results are shown in table 2.
The PA66 spin dope prepared in this example is designated PA66-8.
Comparative example 2
Preparing a PA66 spinning slurry dispersion system: 470g of PA66 powder, 2.5g of alkylbenzene sulfonate and 2g of silane coupling agent were added to a stirring tank and stirred at 450rpm for 45min, then 25g of metal oxide and 5g of MOF, which were not pre-treated and ground, were added and stirring was continued at 600rpm for 3h to prepare a uniformly mixed PA66 spinning dope. In order to ensure spinnability of the spinning dope, the dispersibility of the particles (particle size and particle size distribution) in the spinning dope was measured using a dynamic light scattering analyzer (DLS).
The PA66 spin dope prepared above was labeled PA66-1.2.
In the above examples and comparative examples, the PA66, metal oxide system and MOF material ratios are shown in table 1, as follows:
TABLE 1 composition of the effective components of the Nylon 66 spin dope in case of implementation
| Sample name | PA66 duty cycle | Metal oxide ratio | MOF duty cycle |
| PA66-1 | 94 | 5 | 1 |
| PA66-2 | 98 | 1 | 1 |
| PA66-3 | 95 | 5 | 0 |
| PA66-4 | 97 | 3 | 0 |
| PA66-5 | 99 | 1 | 0 |
| PA66-6 | 99 | 0 | 1 |
| PA66-7 | 99.2 | 0 | 0.8 |
| PA66-8 | 99.4 | 0 | 0.6 |
| PA66-1.1 | 100 | 0 | 0 |
| PA66-1.2 | 94 | 5 | 1 |
After milling, the average particle size of the metal oxide, MOF and PA66 spin-slurry dispersion are shown in table 2 as follows:
TABLE 2 particle size statistics
| Dispersing component | Primary average particle diameter | Average particle diameter after grinding |
| Metal oxide | 300nm | 148nm |
| MOF | 200.0nm | 100.0nm |
| PA66-1 | 3.0μm | / |
| PA66-2 | 3.6μm | / |
| PA66-3 | 3.2μm | / |
| PA66-4 | 3.5μm | / |
| PA66-5 | 3.8μm | / |
| PA66-6 | 3.5μm | / |
| PA66-7 | 3.6μm | / |
| PA66-8 | 3.6μm | / |
| PA66-1.1 | 4.5μm | / |
| PA66-1.2 | 4.9μm | / |
Example 9
The spinning dope prepared in examples 1 to 8 and comparative examples 1 to 2 was melt-spun:
adopting a double-screw extruder, wherein the diameter of the screw is 26mm, and the length-diameter ratio is 52; the spinning operation comprises a pre-spinning process and a post-spinning process; the manufacturer of the twin-screw extruder is Jiangsu Chengyi equipment Co., ltd, and specifically comprises the following steps:
the pre-spinning process comprises the following steps: adding the prepared PA66 spinning slurry into a double-screw extruder, setting the temperature of eight double-screw heating zones, wherein the temperature of the first heating zone is 250 ℃, the temperature of the second heating zone is 265 ℃, the temperature of the third heating zone is 265 ℃, the temperature of the fourth heating zone is 285 ℃, the temperature of the fifth heating zone is 290 ℃, the temperature of the sixth heating zone is 305 ℃, the temperature of the seventh heating zone is 305 ℃, and the temperature of the eighth heating zone is 295 ℃; after the temperature of each heating temperature zone reaches the set temperature, starting and running a water oil pump for 15min, then starting a double-screw extruder, setting the rotating speed of the double screws to 65rpm, adding spinning slurry into a feed inlet, melting a polymer molecular chain under the action of a heating zone of the double-screw extruder, and finally extruding by a spinneret plate to obtain the PA66 nascent fiber.
Post-spinning: and cooling the pre-spun PA66 nascent fiber through the water bath effect of 25 ℃, pre-drawing the cooled fiber through a drawing device, and carrying out multistage hot drawing to obtain the PA66 fiber with excellent mechanical properties.
The PA66 in the spinning slurry is in eight heating areas of a double-screw extruder, and the PA66 molecular chain is entangled and opened to generate orientation rearrangement to generate crystallization through the shearing force provided by the double screws, so that the prepared PA66 primary fiber has good orientation degree and crystallization degree, and the specific surface area and the porosity of the fiber material can be improved due to the addition of MOF with surface effect; the final fiber has the characteristics of large specific surface area and high porosity.
The PA66 fibers prepared in examples 1-8 and comparative examples 1-2 were designated as sample PA66-1, sample PA66-2, sample PA66-3, sample PA66-4, sample PA66-5, sample PA66-6, sample PA66-7, sample PA66-8, and sample PA66-1.1, sample PA66-1.2 in that order.
Material property test
Mechanical property test: and (3) carrying out mechanical property test on the prepared PA66 fiber under a universal stretcher to obtain the tensile breaking strength and the tensile breaking modulus of the tensile property.
Mechanical drawing of PA66 fibers using a universal drawing machinePerformance was tested: clamping the monofilament at the upper and lower ends at a clamping distance of 20mm and a stretching speed of 20mm.min -1 Ten times of sampling are carried out on each fiber in parallel, and the mechanical tensile breaking strength and the initial modulus of the PA66 fiber are obtained by obtaining an average value. In a constant temperature and humidity environment, a PA66 fiber sample is clamped at the upper end and the lower end of a clamp holder, the pre-tension of a machine is set to be 0.05cN/dtex, then a constant force of 25% of fiber breaking load is applied, creep is kept for a period of time, the length of the final fiber is recorded, and the creep rate of the fiber is calculated.
Conducting performance test: conducting performance tests were carried out according to GB T1410-2006 (IEC 60093) solid insulating material volume resistivity and surface resistivity test methods. Placing the prepared PA66 fiber in a conductivity tester for testing to obtain the surface resistivity of the fiber, and characterizing the conductivity of the fiber at one time; the experimental determination results are shown in table 3, as follows:
TABLE 3 mechanical and electrical conductivity of PA66 fibers
| Name of the name | Breaking strength (MPa) | Initial modulus (MPa) | Creep rate (%) | Surface resistivity (Ω) |
| Sample PA66-1 | 149 | 35 | 0.26 | 1×106 |
| Sample PA66-2 | 145 | 33 | 0.28 | 2×106 |
| Sample PA66-3 | 141 | 33 | 0.31 | 3×106 |
| Sample PA66-4 | 138 | 31 | 0.30 | 2×107 |
| Sample PA66-5 | 136 | 30 | 0.30 | 8×107 |
| Sample PA66-6 | 143 | 32 | 0.29 | 3×106 |
| Sample PA66-7 | 142 | 31 | 0.29 | 4×106 |
| Sample PA66-8 | 141 | 30 | 0.30 | 5×106 |
| Sample PA66-1.1 | 126 | 23 | 0.52 | 6×1011 |
| Sample PA66-1.2 | 135 | 29 | 0.46 | 6×1010 |
From the test results in the above table, it can be seen that: the mechanical property and the electric conductivity of the PA66 fiber added with the metal oxide and the MOF are correspondingly improved, wherein the maximum creep rate reduction can reach 50%, and the maximum surface resistivity can be reduced by 5 orders of magnitude.
If only one of metal oxide or MOF is added into the spinning slurry, the performance of the finally prepared PA66 fiber is correspondingly enhanced, but the performance of the fiber prepared by the simultaneous addition of the two components is not superior; the performance test result of the PA66 fiber prepared by the single component can be obtained, and the PA66 fiber prepared by adding trace MOF (0.5% -1.0%) can achieve similar effects on the aspects of mechanical property and conductivity as the PA66 fiber prepared by adding a small amount (1.0% -5.0%) of metal oxide, so that the addition of trace MOF material can produce more obvious modification effect on the final performance of the fiber; when both components are added simultaneously, the performance of the PA66 fiber performs optimally, indicating that both components can exert a dual effect synergistic effect to optimize fiber performance.
In addition, as can be obtained from comparative example 2, when the metal oxide and the MOF are not subjected to pretreatment grinding and directly doped with PA66 to prepare a spinning dope, the mechanical properties and the electrical conductivity of the final PA66 fiber are not improved too much, which indicates that the pretreatment grinding of the metal oxide and the MOF and the doping of PA66 to prepare the spinning dope for spinning can have a very important positive influence on the properties of the final fiber.
The metal oxide and the MOF material are added simultaneously, the mechanical property and the electric conduction property of the PA66 fiber are excellent, the solid content of the PA is increased on the basis, and the property of the final fiber is slightly reduced. Therefore, the metal oxide and the MOF material are added simultaneously, so that the double-effect synergistic effect can be exerted, and the performance of the prepared PA66 fiber is optimal. And the PA solids content variation also has a certain effect on the properties of the final fiber.
In conclusion, the high-strength creep-resistant and antistatic PA66 fiber is successfully prepared by using a melt spinning-super stretching technology process, a metal oxide and MOF (metal oxide fiber) double-effect synergistic effect network is constructed by doping the metal oxide and the MOF in the preparation process of the melt spinning slurry, the orientation arrangement and the crystallinity of a polymer molecular chain are increased, a three-dimensional conductive network is constructed in the fiber, and the creep-resistant performance and the antistatic effect of the PA66 fiber are greatly enhanced. According to the mechanical property test and the conductivity test, when the solid content of PA66 in the spinning solution is 94% and the metal oxide is 5%, the mechanical strength, modulus, creep rate and surface resistivity test result of the PA66 fiber prepared when the MOF material is 1% are optimal.
Although the present invention has been described in detail by way of reference to preferred embodiments, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The spinning slurry for the high-strength creep-resistant antistatic nylon 66 fiber is characterized by comprising the following components in parts by weight:
94-100 parts of PA66 powder, 1-5 parts of metal oxide, 0.5-1 part of Metal Organic Framework (MOF), 0.1-0.5 part of coupling agent, 0.1-0.5 part of surfactant, 0.1-0.5 part of wetting dispersant and 0.2-0.5 part of electrolyte.
2. The spinning dope for high-strength creep-resistant antistatic nylon 66 fiber according to claim 1, wherein the average particle size of the PA66 powder is 5 μm and the bulk density is 0.5g/cm 3 The melting point was 265 ℃.
3. The spinning dope for high-strength creep-resistant antistatic nylon 66 fiber according to claim 1, wherein the metal oxide is one or more of nano iron oxide, nano copper oxide and nano aluminum oxide, and the average particle size of the metal oxide is 300nm.
4. The spin dope for high-strength, creep-resistant and antistatic nylon 66 fiber according to claim 1, wherein the MOF is one or more of MOF-uo-66 (Zr), HKUST-1, ZIF-8 and MILs, and the average particle size of the MOF is 200nm.
5. The spinning dope for high-strength creep-resistant and antistatic nylon 66 fiber according to claim 1, wherein said coupling agent is a silane coupling agent; the silane coupling agent is one or more of trichloroethylene silane, triethoxyvinyl silane, gamma-aminopropyl triethoxy silane and trichloropropenyl silane.
6. The spin dope for high strength, creep-resistant and antistatic nylon 66 fiber according to claim 1, wherein the surfactant type is an anionic surfactant, in particular one or more of alkylbenzene sulfonate, polysiloxane, fatty alcohol polyoxyethylene ether phosphate, polyoxyethylene monolaurate.
7. The spinning dope for high-strength creep-resistant antistatic nylon 66 fiber according to claim 1, wherein said wetting dispersant is diisooctyl sodium sulfosuccinate, the solid content is 70-75%, the pH is 5.0-7.0, and the viscosity is less than 200.
8. The spinning dope for high-strength creep-resistant antistatic nylon 66 fiber according to claim 1, wherein the electrolyte comprises polyaniline and lithium chloride in a mass ratio of 1:1.
9. The method for preparing the spinning dope for the high-strength creep-resistant and antistatic nylon 66 fiber according to claim 1, wherein the process is as follows:
(1) Preparing materials: weighing for standby according to the proportion of each component in the spinning slurry;
(2) Preparation of a metal oxide system:
adding metal oxide and electrolyte into a beaker, adding deionized water, and stirring for 2-3h at room temperature to obtain mixed slurry A; grinding the mixed slurry A in a ball mill for 3-4h to ensure that the average particle size of particles in the mixed slurry A is less than 150nm, and obtaining mixed slurry B with uniform dispersion; filtering the mixed slurry B, and drying a filter cake to obtain a uniformly dispersed metal oxide system for later use;
(3) Preparing MOF material:
adding MOF, wetting dispersant and surfactant into a beaker, stirring at room temperature for 2-3h to obtain a mixture A, then putting the mixture A into a ball mill for ball milling for 3-4h, and stopping milling when the average particle size of the MOF in the mixture A is smaller than 100nm to obtain a mixture B; filtering the mixture B which is qualified in grinding and uniformly dispersed, filtering and drying to obtain MOF material, and bagging for later use;
(4) Preparing a PA66 spinning slurry dispersion system:
adding the PA66 powder, the surfactant and the coupling agent into a stirring barrel, stirring at 300-500rpm for 30-50min, then adding the metal oxide system in the step (2) and the MOF material in the step (3), and continuously stirring at 400-700rpm for 2-3h to obtain the uniformly mixed PA66 spinning slurry.
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