CN112663167A - Flame-retardant polyester fiber and preparation method thereof - Google Patents
Flame-retardant polyester fiber and preparation method thereof Download PDFInfo
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Abstract
The invention aims to provide a flame-retardant PET polyester fiber and a preparation method thereof. The flame-retardant PET polyester fiber consists of the following raw materials: the flame-retardant polyester chip comprises 100-110 parts of polyester chips and 5-8 parts of flame-retardant polyester master batches; the flame-retardant polyester master batch comprises the following components: 8-10 parts of inorganic nanoparticles and 20-30 parts of flame retardant; 2-4 parts of a dispersing agent and 2-4 parts of a coupling agent; 0.2 to 1 part of antioxidant; the rest is polyester granules; and (3) carrying out melt blending spinning on the polyester chips and the flame-retardant polyester master batches by a spinning assembly to perform spinning extrusion, cooling by circular air blowing, bundling and oiling, drafting, heat setting and winding to prepare the flame-retardant polyester fiber. The fluorine-containing flame retardant with excellent flame retardant effect is synthesized and applied to the preparation of the flame-retardant PET polyester fiber, and the prepared PET polyester fiber has excellent flame retardant property and good comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of flame-retardant fibers, and particularly relates to a flame-retardant polyester fiber and a preparation method thereof.
Background
Polyethylene terephthalate (PET) was the earliest linear thermoplastic polymer commercialized by DuPont, usa. The high-performance composite material has excellent physical performance and mechanical performance maintained in a wide temperature range, excellent friction resistance, excellent ageing resistance, excellent fatigue resistance and excellent electric insulating property, is insoluble in most organic solvents and inorganic acids, has good processing performance and low production energy consumption, and is widely used for plastic packaging bottles, films, synthetic fibers and the like.
The polyester fiber is polyethylene terephthalate (PET) fiber, has excellent performance, easily obtained raw materials and wide application, is a synthetic fiber with the fastest development, the highest yield and the widest application range in various synthetic fibers, and is known as the king of fiber in the 21 st century. Polyester fibers have excellent properties such as high strength, dimensional stability, chemical resistance, and the like, and have very wide applications in the fields of clothing, carpets, and decorative fabrics. However, polyester fibers are melt-combustible fibers, and it is important to perform flame-retardant treatment on polyester fibers to reduce the risk of the polyester fabric in fire.
Generally, the flame retardance of polyester fibers is realized by flame retardance modification or surface treatment modification of strands, and the specific method can be summarized into the following five ways:
(1) copolymerization of flame-retardant monomers: flame retardant elements such as halogen, phosphorus or sulfur are introduced into monomer dibasic acid or dihydric alcohol molecules for synthesizing the polyester, and then the polyester is synthesized. The method has the advantages of lasting flame retardant property and washing resistance, and has the defects of slightly complex process, high development cost of the copolymerization type flame retardant and large influence on the performance of the polyester.
(2) Blending flame-retardant modification: the method is to spin after blending and granulating common polyester and fire retardant, and is simple and easy to implement and low in operation cost because the change of polymerization production process is not involved, but the fire retardant durability of the fiber is inferior to that of the copolymerization modification method. However, the added flame retardant must have good compatibility with the polyester and high thermal stability. At present, small molecular organic matters or inorganic matters are mostly adopted as additives in China, the addition amount is large, and the influence on the spinnability and the mechanical property of the fiber is large.
(3) Composite spinning flame-retardant modification: the flame retardance of polyester is realized by changing a spinning process, and a sheath-core structure with flame-retardant polyester as a core and polyester as a sheath is adopted in spinning generally. Thus, the flame retardant can be prevented from being decomposed prematurely, the requirement on the thermal stability of the flame retardant is reduced, and the original performance of the fiber can be maintained. However, this method requires complicated spinning equipment, which limits its application.
(4) Polyester fiber grafting modification: the method grafts the reactive flame retardant on the polyester fiber (mainly surface grafting), the flame retardant efficiency depends on the chemical structure and the grafting part of the flame retardant, and the method can be realized by chemical and plasma methods. However, the method has high requirements on technical conditions, a complex process route and difficult industrialization.
(5) Flame-retardant finishing of polyester fabric: polyester fabric is soaked or padded in a solution containing a flame retardant, and then crosslinking is carried out to form a layer of film on the outer layer of the fabric so as to achieve the flame retardant effect, but the flame retardant durability is not high, and the fabric has poor hand feeling; meanwhile, the physical properties of the fiber are damaged to a certain extent, and the processing cost is higher.
Therefore, the development of a flame retardant PET polyester fiber is becoming a hot spot for the development and research of functional polyester materials.
Disclosure of Invention
The invention aims to provide a flame-retardant PET polyester fiber and a preparation method thereof. The fluorine-containing flame retardant with excellent flame retardant effect is synthesized and applied to the preparation of the flame-retardant PET polyester fiber, and the prepared PET polyester fiber has excellent flame retardant property and good comprehensive performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a flame-retardant polyester fiber which comprises the following raw materials in parts by weight: the flame-retardant polyester chip comprises 100-110 parts of polyester chips and 5-8 parts of flame-retardant polyester master batches; the flame-retardant polyester master batch comprises the following components: 8-10 parts of inorganic nanoparticles and 20-30 parts of flame retardant; 2-4 parts of a dispersing agent and 2-4 parts of a coupling agent; 0.2 to 1 part of antioxidant; the rest is polyester granules;
the polyester chip is a PET polyester chip; the polyester granules are PET polyester granules; the invention aims at the modification of PET polyester and aims at preparing PET polyester fiber with good flame retardant property;
the flame retardant is a fluorine-containing flame retardant; the fluorine-containing flame retardant has the advantages that C-F bond energy is large, decomposition temperature is high, fluorine atoms are not flammable, and the material has good carbon forming property and better flame retardant property; in the prior art, a direct polymerization method such as fluorine-containing monomers shown in fig. 1 and fig. 2 is generally adopted to directly polymerize flame-retardant polyester, but the performance of PET polyester is greatly influenced; the invention blends and granulates common polyester and flame retardant and then spins, and is simple and easy to operate and low in operation cost because the invention does not relate to the change of polymerization production process.
The inorganic nanoparticles contain silica aerogel nanoparticles. In the process of cooling, inorganic nanoparticles are present in the PET melt as second-phase small particles, and PET molecular chains take the particles as centers and are adsorbed on the particles to be orderly arranged to form crystal nuclei. The inorganic nucleating agent is added, so that the heterogeneous nucleation capability of PET at high temperature can be improved, the crystallization rate is accelerated, and the uniformity of the grain size and the structure can be improved.
The particle size of the inorganic nanoparticles is 200-700 nm; the surface atoms of the nano particles have a plurality of dangling bonds and have unsaturated properties, so that the nano particles are easy to combine with other atoms to tend to be stable and have high chemical activity. For a modified PET polyester composite system, the smaller the aggregate of the nano particles, the better the aggregate, and the more obvious the reinforcing and toughening effect; the aggregation of the nanoparticles beyond a certain size can make the composite system lose its meaning.
Preferably, the coupling agent is a silicon coupling agent, a phosphate coupling agent or an aluminate coupling agent; the dispersing agent is polyethylene glycol, trimethylolethane or polyvinylpyrrolidone; the antioxidant is hindered phenol antioxidant 1010.
Preferably, the preparation method of the fluorine-containing flame retardant comprises the following steps: heating hexachlorocyclotriphosphazene, hydroxyl fluorosilicone oil and sodium hydroxide in tetrahydrofuran for reaction for a period of time, cooling to normal temperature, slowly adding a tetrahydrofuran solution of sodium phenolate, heating for reaction for a period of time, performing rotary evaporation to remove the tetrahydrofuran solvent, washing with water, washing with deionized water to remove NaCl and sodium phenolate impurities, purifying with trichloromethane, and performing rotary evaporation on a purified product to obtain a tawny product, namely the fluorine-containing flame retardant, wherein the test data is shown in figure 2. The fluorine-containing flame retardant prepared by the invention contains fluorine-silicon oil base, and Si-O-of the fluorine-silicon oil base can play a lubricating role in the chain segment movement of PET, so that the chain segment movement of the PET is easier, the flexibility of the PET is improved, and the crystallization rate is further improved.
Preferably, the mole ratio of the hexachlorocyclotriphosphazene, the hydroxyfluorosilicone oil, the sodium hydroxide and the sodium phenolate is 1: 1: 1: 6-7; the reaction time is 20-24 hours.
FIG. 3 is an FTIR spectrum of a fluorinated flame retardant synthesized in accordance with the present invention. As can be seen from FIG. 3, the length of the groove is 1266, 1176 cm-1' at the characteristic absorption peak of P = N bond of phosphazene skeleton, at 2931 cm-1The position is a stretching vibration absorption peak of saturated C-H bonds on the fluorosilicone oil, which proves that the grafting of the hydroxyl fluorosilicone oil on the product is successful, and is 3060 cm-1The peak is the vibration absorption peak of unsaturated C-H bond in benzene ring, which is 1592 cm-1And 1488 cm-1The position is a skeleton deformation vibration absorption peak of a benzene ring, 766 cm to 689 cm-1The position is a mono-substituted bending vibration absorption peak of a benzene ring, which shows that the phenoxy is successfully connected to the cyclotriphosphazene. 601, 530 cm-1The vibration absorption peak of the P-Cl bond at (A) is substantially disappeared, indicating that the chlorine atom on the phosphazene structure is substantially completely substituted. In conclusion, a novel fluorine-containing flame retardant is synthesized.
Preferably, the inorganic nanoparticles are composite nanoparticles of silica aerogel and titanium dioxide. The titanium dioxide nano particles have photocatalytic oxidation antibacterial action, and electrons (e) on the valence band of the oxide of the titanium dioxide nano particles are generated under a certain illumination condition-) Excited transition to the conduction band leaving a positively charged hole (H)+），e-And H+With O adsorbed on the surface of the material2-OH and H2O, etc. to produce OH-、O2 -. In which OH has a very strong oxidizing activity-Can decompose various components of microorganism (such as unsaturated bond in bacterial body cell, chain reaction is excited by newly generated free radical, polypeptide chain of bacterial protein is broken, and saccharide is depolymerized), thereby achieving bactericidal effect. At the same time, O2 -Stronger reducibility also plays an antibacterial role.
The invention also provides a preparation method of the flame-retardant polyester fiber, and the flame-retardant polyester fiber is prepared by carrying out melt blending spinning on the polyester chips and the flame-retardant polyester master batches through a spinning assembly, carrying out spinning extrusion, cooling by circular blowing, bundling and oiling, drafting, heat setting and winding.
Preferably, the melt blending spinning temperature is 274-286 ℃, the air temperature of circular blowing is 26-29 ℃, and the air speed of circular blowing is 0.3-0.5 m/min; the stretching ratio is 2.7-3.5 times, the stretching temperature is 146-164 ℃, the heat setting temperature is 135-150 ℃, and the winding speed is 4000-4500 m/min.
Preferably, the preparation method of the flame-retardant polyester master batch comprises the following steps: the flame-retardant polyester master batch is prepared by mixing the components in proportion by weight, adding the mixture into a high-speed mixer with the rotating speed of 500-1500 rpm, mixing the mixture for 10-20 minutes at the mixing temperature of 140-180 ℃, adding the mixed material into a double-screw extruder for melt blending, controlling the melting temperature to be 270-290 ℃ and the rotating speed of screws to be 100-300 rpm, shearing and mixing the mixture for 10-15 minutes through the double-screw extruder, extruding, cooling, granulating, drying and packaging.
Preferably, the preparation method of the composite nanoparticle of silica aerogel and titanium dioxide comprises the following steps: adding silicon aerogel nanoparticles into deionized water, performing ultrasonic treatment for 5-10 minutes, removing the deionized water (centrifugal dewatering can be adopted), performing quick freezing (the step aims to enable the silicon aerogel nanoparticles to contain water), preparing silicon aerogel nanoparticles containing ice blocks, slowly dropping titanium tetrachloride into the silicon aerogel nanoparticles containing ice blocks, usually dropping 1 drop of titanium tetrachloride into 0.1g of aerogel (the step aims to enable the titanium tetrachloride to react with the silicon aerogel nanoparticles containing water, so that titanium dioxide is generated in the pore diameter of the silicon aerogel nanoparticles, meanwhile, because the water in the silicon aerogel nanoparticles is chilled water, the reaction rate of the titanium dioxide and the titanium dioxide is low, drying the silicon aerogel nanoparticles at 60-70 ℃ for 20-30 minutes, then placing the silicon aerogel nanoparticles into a muffle furnace, heating the silicon aerogel nanoparticles to 400 ℃ for sintering, and preparing the composite nanoparticles of the silicon aerogel and the titanium dioxide, because the silica aerogel is lighter, is easy to float in a solvent and is difficult to disperse, the titanium dioxide particles are introduced into the pore diameter of the silica aerogel nanoparticles to increase the weight of the silica aerogel nanoparticles, thereby being beneficial to subsequent dispersion; on the other hand, the titanium dioxide particles are generated in the pore diameter of the silica aerogel nanoparticles, which effectively limits the particle size of the titanium dioxide particles (the corresponding particle size range is 200-700nm, as shown in fig. 4), the titanium dioxide particles with small particle size have higher catalytic activity and better antibacterial activity (the antibacterial principle is shown in fig. 5).
Preferably, the heating curve in the muffle furnace is that the temperature rises to 200 degrees at a temperature rise rate of 5 degrees per minute, and then rises from 200 degrees to 400 degrees at a temperature rise rate of 2 degrees per minute. (after heating, firstly, the water in the silica aerogel nano particles can be removed, but the crystal form of the titanium dioxide can be changed from rutile type to anatase type, thereby leading the catalytic effect to be better)
Preferably, the sintered composite nano particles of silica aerogel and titanium dioxide are rapidly cooled in liquid nitrogen for 5-10S, and the purpose of quenching is to pre-cool and burst the surfaces of titanium dioxide particles to form more surface defect states, so that the photocatalytic performance of titanium dioxide is improved, the antibacterial performance of titanium dioxide is also improved, and the composite nano particles of silica aerogel and titanium dioxide are reduced, and the data shows that the particle sizes of the silica aerogel and the titanium dioxide are about 100nm, as shown in fig. 6.
Advantageous effects
1. The fluorine-containing flame retardant prepared by the invention belongs to cyclotriphosphazene flame retardants, and releases a large amount of CO in the combustion process2，NH3And N2And the like, and the fluorine-containing flame retardant has large C-F bond energy, high decomposition temperature and non-flammable fluorine atoms, so that the material has good carbon forming property and better flame retardant property.
2. The invention also adds inorganic nano particles as second phase small particles existing in the PET melt, and PET molecular chains take the particles as centers and are adsorbed on the particles to be orderly arranged to form crystal nuclei. The inorganic nucleating agent is added, so that the heterogeneous nucleation capability of PET at high temperature can be improved, the crystallization rate is accelerated, the uniformity of the grain size and the structure can be improved, and the problem of poor crystallization performance of PET polyester can be effectively solved.
3. The invention blends and granulates common polyester, fire retardant, inorganic particles and the like, and then spins, and is simple and easy to operate and low in operation cost because the invention does not relate to the change of polymerization production process.
4. The added inorganic nano particles can be composite nano particles of silica aerogel and titanium dioxide, wherein the titanium dioxide nano particles have photocatalytic oxidation and bacteriostasis functions, so that the polyester fiber has an antibacterial function.
5. The fluorine-containing flame retardant and the inorganic nanoparticles have a synergistic effect, on one hand, the fluorine-containing flame retardant and the inorganic nanoparticles both contain Si-O bonds, the fluorine-containing flame retardant is used as a surfactant of the inorganic nanoparticles to increase the compatibility of the inorganic nanoparticles and PET polyester, and meanwhile, the addition of the fluorine-containing flame retardant can influence the crystallinity of the PET polyester, and the inorganic nanoparticles can improve the effect, so that the fluorine-containing flame retardant and the inorganic nanoparticles have a synergistic effect.
6. The composite nano particles of the silica aerogel and the titanium dioxide are prepared, and the silica aerogel is lighter, is easy to float in a solvent and is difficult to disperse; on the other hand, the titanium dioxide particles are generated in the pore diameter of the silica aerogel nanoparticles, so that the particle size of the titanium dioxide particles is effectively limited, the titanium dioxide particles with small particle size have higher catalytic activity and better antibacterial activity.
Drawings
FIG. 1 is a schematic representation of a prior art fluoromonomer;
FIG. 2 is a schematic representation of a prior art fluoropolyester;
FIG. 3 is test data for a fluorine-containing flame retardant of the present invention
FIG. 4 is a graph of the particle size distribution of composite nanoparticles of silica aerogel and titanium dioxide in accordance with the present invention;
FIG. 5 is a schematic view of the antibacterial effect of polyester fiber according to the present invention;
FIG. 6 is an SEM image of a composite nanoparticle of silica aerogel and titanium dioxide of the present invention after a shock freezing process;
FIG. 7 is a table of basic performance data for polyester fibers of the present invention;
FIG. 8 is a table of the antibacterial data of the polyester fiber of the present invention.
Detailed Description
Example 1
A preparation method of flame-retardant polyester fiber comprises the following steps:
the preparation method of the composite nano particle of the silica aerogel and the titanium dioxide comprises the following steps: adding the silica aerogel nano particles into deionized water, carrying out ultrasonic treatment for 5 minutes, removing the deionized water, carrying out quick freezing to obtain silica aerogel nano particles containing ice blocks, slowly dripping titanium tetrachloride into the silica aerogel nano particles containing the ice blocks, drying at 60 ℃ for 20 minutes, then putting into a muffle furnace, heating to 400 ℃, putting into the muffle furnace, heating according to a heating rate of 5 ℃ per minute to 200 ℃, and then heating from 200 ℃ to 400 ℃ according to a heating rate of 2 ℃ per minute to obtain the composite nano particles of silica aerogel and titanium dioxide.
The preparation method of the fluorine-containing flame retardant comprises the following steps: 60mL of tetrahydrofuran was added to a three-necked flask, and hexachlorocyclotriphosphazene (0.04 mol) and sodium hydroxide (0.04 mol) were weighed and charged into the three-necked flask, followed by stirring until hexachlorocyclotriphosphazene was completely dissolved. Slowly dripping (0.04 mol of hydroxyl) hydroxyl fluorosilicone oil into a three-neck flask through a constant pressure dropping funnel, heating to 65 ℃, and reacting for 20 hours. Meanwhile, phenol (0.12 mol) is added into 40mL tetrahydrofuran, 5.52g of metallic sodium is weighed and put into the tetrahydrofuran solution of phenol in the form of fine chips, and the tetrahydrofuran solution of sodium phenolate is obtained after the sodium is completely disappeared. At normal temperature, a tetrahydrofuran solution of sodium phenolate was slowly dropped into the three-necked flask through a constant pressure dropping funnel. After the dropwise addition, slowly raising the temperature to 65 ℃, and continuing the reaction for 20 hours to obtain a milky white liquid. Removing tetrahydrofuran solvent by rotary evaporation, washing off impurities such as NaCl, sodium phenolate and the like by using deionized water, purifying by using trichloromethane, and carrying out rotary evaporation on a purified substance to obtain a tawny product, namely the fluorine-containing flame retardant.
The preparation method of the flame-retardant polyester master batch comprises the following steps: 10 parts of composite nano particles of silicon aerogel and titanium dioxide, which have the particle size of 200-700nm, and 30 parts of fluorine-containing flame retardant; 4 parts of dispersant polyethylene glycol and 2-4 parts of phosphate coupling agent; 10101 parts of hindered phenol antioxidant; the rest is PET polyester granules; then adding the mixture into a high-speed mixer with the rotating speed of 1500 rpm, mixing for 20 minutes at the mixing temperature of 180 ℃, adding the mixed materials into a double-screw extruder for melt blending, controlling the melting temperature at 290 ℃ and the rotating speed of the screw at 300 rpm, shearing and mixing for 15 minutes by the double-screw extruder, then extruding, cooling, pelletizing, drying and packaging to obtain the flame-retardant polyester master batch.
And (3) carrying out melt blending spinning on 100 parts of PET polyester chips and 5 parts of flame-retardant polyester master batches by a spinning assembly, carrying out spinning extrusion, cooling by circular air blowing, bundling and oiling, drafting, carrying out heat setting and winding to prepare the flame-retardant polyester fiber. The melt blending spinning temperature is 274 ℃, the air temperature of circular blowing is 26 ℃, and the air speed of the circular blowing is 0.3 m/min; the stretching ratio is 2.7 times, the stretching temperature is 146 ℃, the heat setting temperature is 135 ℃, and the winding speed is 4000 m/min.
The limit oxygen index of the flame-retardant polyester fiber prepared by the invention reaches 28%, and the vertical combustion reaches V-0 level.
Example 2
A preparation method of flame-retardant polyester fiber comprises the following steps:
the preparation method of the composite nano particle of the silica aerogel and the titanium dioxide comprises the following steps: adding the silica aerogel nano particles into deionized water, carrying out ultrasonic treatment for 10 minutes, removing the deionized water, carrying out quick freezing to obtain silica aerogel nano particles containing ice blocks, slowly dripping titanium tetrachloride into the silica aerogel nano particles containing the ice blocks, drying at 70 ℃ for 30 minutes, then putting into a muffle furnace, heating to 400 ℃, putting into the muffle furnace, heating according to a heating rate of 5 ℃ per minute to 200 ℃, and then heating according to a heating rate of 2 ℃ per minute from 200 ℃ to 400 ℃, thus obtaining the composite nano particles of silica aerogel and titanium dioxide.
The preparation method of the fluorine-containing flame retardant comprises the following steps: 60mL of tetrahydrofuran was added to a three-necked flask, and hexachlorocyclotriphosphazene (0.04 mol) and sodium hydroxide (0.04 mol) were weighed and charged into the three-necked flask, followed by stirring until hexachlorocyclotriphosphazene was completely dissolved. Slowly dripping (0.04 mol of hydroxyl) hydroxyl fluorosilicone oil into a three-neck flask through a constant pressure dropping funnel, heating to 65 ℃, and reacting for 24 hours. Meanwhile, phenol (0.14 mol) is added into 40mL tetrahydrofuran, 5.52g of metallic sodium is weighed and put into the tetrahydrofuran solution of phenol in the form of fine chips, and the tetrahydrofuran solution of sodium phenolate is obtained after the sodium is completely disappeared. At normal temperature, a tetrahydrofuran solution of sodium phenolate was slowly dropped into the three-necked flask through a constant pressure dropping funnel. After the dropwise addition, slowly raising the temperature to 65 ℃, and continuing the reaction for 24 hours to obtain milky white liquid. Removing tetrahydrofuran solvent by rotary evaporation, washing off impurities such as NaCl, sodium phenolate and the like by using deionized water, purifying by using trichloromethane, and carrying out rotary evaporation on a purified substance to obtain a tawny product, namely the fluorine-containing flame retardant.
The preparation method of the flame-retardant polyester master batch comprises the following steps: 8 parts of composite nano particles of silicon aerogel and titanium dioxide, the particle size of the composite nano particles is 200-700nm, and 20 parts of fluorine-containing flame retardant; 2 parts of dispersant trimethylolethane and 2 parts of silicon coupling agent; 10100.2 parts of hindered phenol antioxidant; the rest is PET polyester granules; and then adding the mixture into a high-speed mixer with the rotating speed of 500 revolutions per minute, mixing for 10 minutes at the mixing temperature of 140 ℃, adding the mixed materials into a double-screw extruder for melt blending, controlling the melting temperature at 270 ℃ and the rotating speed of the screws at 100-300 revolutions per minute, shearing and mixing for 1 minute through the double-screw extruder, and then extruding, cooling, pelletizing, drying and packaging to obtain the flame-retardant polyester master batch.
And (3) carrying out melt blending spinning on 107 parts of PET polyester chips and 7 parts of flame-retardant polyester master batches by using a spinning assembly for spinning extrusion, cooling by circular air blowing, bundling and oiling, drafting, carrying out heat setting and winding to prepare the flame-retardant polyester fiber. The melt blending spinning temperature is 286 ℃, the circular blowing air temperature is 29 ℃, and the circular blowing air speed is 0.5 m/min; the stretching ratio was 3.5 times, the stretching temperature was 164 ℃, the heat-setting temperature was 150 ℃, and the winding speed was 4500 m/min.
The limit oxygen index of the flame-retardant polyester fiber prepared by the invention reaches 29 percent, and the vertical combustion reaches V-0 level.
Example 3
A preparation method of flame-retardant polyester fiber comprises the following steps:
the preparation method of the composite nano particle of the silica aerogel and the titanium dioxide comprises the following steps: adding the silica aerogel nanoparticles into deionized water, performing ultrasonic treatment for 8 minutes, removing the deionized water, performing quick freezing to obtain silica aerogel nanoparticles containing ice blocks, slowly dripping titanium tetrachloride into the silica aerogel nanoparticles containing ice blocks, drying at 65 ℃ for 28 minutes, then placing the silica aerogel nanoparticles into a muffle furnace to be heated to 400 ℃, placing the muffle furnace to be heated to 200 ℃ according to a heating rate of 5 ℃ per minute, and then heating from 200 ℃ to 400 ℃ according to a heating rate of 2 ℃ per minute to obtain the composite nanoparticles of silica aerogel and titanium dioxide.
The preparation method of the fluorine-containing flame retardant comprises the following steps: 60mL of tetrahydrofuran was added to a three-necked flask, and hexachlorocyclotriphosphazene (0.04 mol) and sodium hydroxide (0.04 mol) were weighed and charged into the three-necked flask, followed by stirring until hexachlorocyclotriphosphazene was completely dissolved. Slowly dripping (0.04 mol of hydroxyl) hydroxyl fluorosilicone oil into a three-neck flask through a constant pressure dropping funnel, heating to 65 ℃, and reacting for 23 hours. Meanwhile, phenol (0.13 mol) is added into 40mL tetrahydrofuran, 5.52g of metallic sodium is weighed and put into the tetrahydrofuran solution of phenol in the form of fine chips, and the tetrahydrofuran solution of sodium phenolate is obtained after the sodium is completely disappeared. At normal temperature, a tetrahydrofuran solution of sodium phenolate was slowly dropped into the three-necked flask through a constant pressure dropping funnel. After the dropwise addition, slowly raising the temperature to 65 ℃, and continuing the reaction for 22 hours to obtain milky white liquid. Removing tetrahydrofuran solvent by rotary evaporation, washing off impurities such as NaCl, sodium phenolate and the like by using deionized water, purifying by using trichloromethane, and carrying out rotary evaporation on a purified substance to obtain a tawny product, namely the fluorine-containing flame retardant.
The preparation method of the flame-retardant polyester master batch comprises the following steps: 9 parts of composite nano particles of inorganic nano particle silicon aerogel and titanium dioxide, the particle size of which is 200-700nm, and 28 parts of fluorine-containing flame retardant; 3 parts of dispersant polyvinylpyrrolidone and 3 parts of aluminate coupling agent; 10100.5 parts of hindered phenol antioxidant; the rest is PET polyester granules; and then adding the mixture into a high-speed mixer with the rotating speed of 1000 revolutions per minute, mixing for 16 minutes at the mixing temperature of 160 ℃, adding the mixed materials into a double-screw extruder for melt blending, controlling the melting temperature at 280 ℃ and the rotating speed of the screws at 200 revolutions per minute, shearing and mixing for 13 minutes through the double-screw extruder, and then extruding, cooling, pelletizing, drying and packaging to obtain the flame-retardant polyester master batch.
And (3) carrying out melt blending spinning on 105 parts of PET polyester chips and 6 parts of flame-retardant polyester master batches by using a spinning assembly for spinning extrusion, cooling by circular air blowing, bundling and oiling, drafting, carrying out heat setting and winding to prepare the flame-retardant polyester fiber. The melt blending spinning temperature is 280 ℃, the circular blowing air temperature is 27 ℃, and the circular blowing air speed is 0.4 m/min; the stretching ratio was 3 times, the stretching temperature was 154 ℃, the heat-setting temperature was 140 ℃, and the winding speed was 4200 m/min.
The limit oxygen index of the flame-retardant polyester fiber prepared by the invention reaches 29.5 percent, and the vertical combustion reaches V-0 grade.
Example 4
A preparation method of flame-retardant polyester fiber comprises the following steps:
the preparation method of the composite nano particle of the silica aerogel and the titanium dioxide comprises the following steps: adding the silica aerogel nanoparticles into deionized water, performing ultrasonic treatment for 9 minutes, removing the deionized water, performing quick freezing to obtain silica aerogel nanoparticles containing ice blocks, slowly dripping titanium tetrachloride into the silica aerogel nanoparticles containing ice blocks, drying at 66 ℃ for 23 minutes, then placing the silica aerogel nanoparticles into a muffle furnace to heat to 400 ℃, placing the muffle furnace to heat to 200 ℃ according to a heating rate of 5 ℃ per minute, and then heating to 400 ℃ from 200 ℃ according to a heating rate of 2 ℃ per minute to obtain the composite nanoparticles of silica aerogel and titanium dioxide.
The preparation method of the fluorine-containing flame retardant comprises the following steps: 60mL of tetrahydrofuran was added to a three-necked flask, and hexachlorocyclotriphosphazene (0.04 mol) and sodium hydroxide (0.04 mol) were weighed and charged into the three-necked flask, followed by stirring until hexachlorocyclotriphosphazene was completely dissolved. Slowly dripping (0.04 mol of hydroxyl) hydroxyl fluorosilicone oil into a three-neck flask through a constant pressure dropping funnel, heating to 65 ℃, and reacting for 21 hours. Meanwhile, phenol (0.12 mol) is added into 40mL tetrahydrofuran, 5.52g of metallic sodium is weighed and put into the tetrahydrofuran solution of phenol in the form of fine chips, and the tetrahydrofuran solution of sodium phenolate is obtained after the sodium is completely disappeared. At normal temperature, a tetrahydrofuran solution of sodium phenolate was slowly dropped into the three-necked flask through a constant pressure dropping funnel. After the dropwise addition, slowly raising the temperature to 65 ℃, and continuing the reaction for 23 hours to obtain a milky white liquid. Removing tetrahydrofuran solvent by rotary evaporation, washing off impurities such as NaCl, sodium phenolate and the like by using deionized water, purifying by using trichloromethane, and carrying out rotary evaporation on a purified substance to obtain a tawny product, namely the fluorine-containing flame retardant.
The preparation method of the flame-retardant polyester master batch comprises the following steps: 9 parts of composite nano particles of silicon aerogel and titanium dioxide, the particle size of which is 200-700nm, and 23 parts of fluorine-containing flame retardant; 4 parts of trimethylolethane and 2.5 parts of phosphate coupling agent; 10100.6 parts of hindered phenol antioxidant; the rest is PET polyester granules; and then adding the mixture into a high-speed mixer with the rotating speed of 1200 r/min, mixing for 18 min at the mixing temperature of 160 ℃, adding the mixed materials into a double-screw extruder for melt blending, controlling the melting temperature at 280 ℃ and the rotating speed of the screws at 200 r/min, shearing and mixing for 13 min through the double-screw extruder, and then extruding, cooling, pelletizing, drying and packaging to obtain the flame-retardant polyester master batch.
And (3) carrying out melt blending spinning on 105 parts of PET polyester chips and 7 parts of flame-retardant polyester master batches by using a spinning assembly for spinning extrusion, cooling by circular air blowing, bundling and oiling, drafting, carrying out heat setting and winding to prepare the flame-retardant polyester fiber. The melt blending spinning temperature is 277 ℃, the air temperature of circular blowing is 28 ℃, and the air speed of the circular blowing is 0.4 m/min; the stretching ratio was 3.0 times, the stretching temperature was 154 ℃, the heat-setting temperature was 139 ℃ and the winding speed was 4200 m/min.
The limit oxygen index of the flame-retardant polyester fiber prepared by the invention reaches 30 percent, and the vertical combustion reaches V-0 level.
Example 5
A preparation method of flame-retardant polyester fiber comprises the following steps:
the preparation method of the fluorine-containing flame retardant comprises the following steps: 60mL of tetrahydrofuran was added to a three-necked flask, and hexachlorocyclotriphosphazene (0.04 mol) and sodium hydroxide (0.04 mol) were weighed and charged into the three-necked flask, followed by stirring until hexachlorocyclotriphosphazene was completely dissolved. Slowly dripping (0.04 mol of hydroxyl) hydroxyl fluorosilicone oil into a three-neck flask through a constant pressure dropping funnel, heating to 65 ℃, and reacting for 22 hours. Meanwhile, phenol (0.13 mol) is added into 40mL tetrahydrofuran, 5.52g of metallic sodium is weighed and put into the tetrahydrofuran solution of phenol in the form of fine chips, and the tetrahydrofuran solution of sodium phenolate is obtained after the sodium is completely disappeared. At normal temperature, a tetrahydrofuran solution of sodium phenolate was slowly dropped into the three-necked flask through a constant pressure dropping funnel. After the dropwise addition, slowly raising the temperature to 65 ℃, and continuing the reaction for 22 hours to obtain milky white liquid. Removing tetrahydrofuran solvent by rotary evaporation, washing off impurities such as NaCl, sodium phenolate and the like by using deionized water, purifying by using trichloromethane, and carrying out rotary evaporation on a purified substance to obtain a tawny product, namely the fluorine-containing flame retardant.
The preparation method of the flame-retardant polyester master batch comprises the following steps: 8.5 parts of silica aerogel nano particles with the particle size of 200-700nm and 27 parts of fluorine-containing flame retardant; 3.5 parts of dispersant polyvinylpyrrolidone and 4 parts of silicon coupling agent; 10100.8 parts of hindered phenol antioxidant; the rest is PET polyester granules; and then adding the mixture into a high-speed mixer with the rotating speed of 900 revolutions per minute, mixing for 18 minutes at the mixing temperature of 170 ℃, adding the mixed materials into a double-screw extruder for melt blending, controlling the melting temperature at 280 ℃ and the rotating speed of the screws at 250 revolutions per minute, shearing and mixing for 14 minutes through the double-screw extruder, and then extruding, cooling, pelletizing, drying and packaging to obtain the flame-retardant polyester master batch.
And (3) carrying out melt blending spinning on 100-110 parts of PET polyester chips and 6 parts of flame-retardant polyester master batches by a spinning assembly, carrying out spinning extrusion, cooling by circular air blowing, bundling and oiling, drafting, carrying out heat setting and winding to prepare the flame-retardant polyester fiber. The melt blending spinning temperature is 280 ℃, the circular blowing air temperature is 28 ℃, and the circular blowing air speed is 0.45 m/min; the stretching ratio is 3.2 times, the stretching temperature is 155 ℃, the heat setting temperature is 140 ℃, and the winding speed is 4300 m/min.
The limit oxygen index of the flame-retardant polyester fiber prepared by the invention reaches 27 percent, and the vertical combustion reaches V-0 level.
Comparative example 1
A preparation method of flame-retardant polyester fiber comprises the following steps:
the preparation method of the composite nano particle of the silica aerogel and the titanium dioxide comprises the following steps: slowly dripping titanium tetrachloride into ice blocks, then adding the silica aerogel nanoparticles, drying for 23 minutes at 66 ℃, then putting the ice blocks into a muffle furnace to be heated to 400 ℃, putting the ice blocks into the muffle furnace to be heated according to the curve that the temperature rises to 200 ℃ at the rate of 5 ℃ per minute, and then rising from 200 ℃ to 400 ℃ at the rate of 2 ℃ per minute to prepare the composite nanoparticles of silica aerogel and titanium dioxide.
The preparation method of the fluorine-containing flame retardant comprises the following steps: 60mL of tetrahydrofuran was added to a three-necked flask, and hexachlorocyclotriphosphazene (0.04 mol) and sodium hydroxide (0.04 mol) were weighed and charged into the three-necked flask, followed by stirring until hexachlorocyclotriphosphazene was completely dissolved. Slowly dripping (0.04 mol of hydroxyl) hydroxyl fluorosilicone oil into a three-neck flask through a constant pressure dropping funnel, heating to 65 ℃, and reacting for 21 hours. Meanwhile, phenol (0.12 mol) is added into 40mL tetrahydrofuran, 5.52g of metallic sodium is weighed and put into the tetrahydrofuran solution of phenol in the form of fine chips, and the tetrahydrofuran solution of sodium phenolate is obtained after the sodium is completely disappeared. At normal temperature, a tetrahydrofuran solution of sodium phenolate was slowly dropped into the three-necked flask through a constant pressure dropping funnel. After the dropwise addition, slowly raising the temperature to 65 ℃, and continuing the reaction for 23 hours to obtain a milky white liquid. Removing tetrahydrofuran solvent by rotary evaporation, washing off impurities such as NaCl, sodium phenolate and the like by using deionized water, purifying by using trichloromethane, and carrying out rotary evaporation on a purified substance to obtain a tawny product, namely the fluorine-containing flame retardant.
The preparation method of the flame-retardant polyester master batch comprises the following steps: 9 parts of composite nano particles of silicon aerogel and titanium dioxide, the particle size of which is 200-700nm, and 23 parts of fluorine-containing flame retardant; 4 parts of trimethylolethane and 2.5 parts of phosphate coupling agent; 10100.6 parts of hindered phenol antioxidant; the rest is PET polyester granules; and then adding the mixture into a high-speed mixer with the rotating speed of 1200 r/min, mixing for 18 min at the mixing temperature of 160 ℃, adding the mixed materials into a double-screw extruder for melt blending, controlling the melting temperature at 280 ℃ and the rotating speed of the screws at 200 r/min, shearing and mixing for 13 min through the double-screw extruder, and then extruding, cooling, pelletizing, drying and packaging to obtain the flame-retardant polyester master batch.
And (3) carrying out melt blending spinning on 105 parts of PET polyester chips and 7 parts of flame-retardant polyester master batches by using a spinning assembly for spinning extrusion, cooling by circular air blowing, bundling and oiling, drafting, carrying out heat setting and winding to prepare the flame-retardant polyester fiber. The melt blending spinning temperature is 277 ℃, the air temperature of circular blowing is 28 ℃, and the air speed of the circular blowing is 0.4 m/min; the stretching ratio was 3.0 times, the stretching temperature was 154 ℃, the heat-setting temperature was 139 ℃ and the winding speed was 4200 m/min.
The limit oxygen index of the flame-retardant polyester fiber prepared by the invention reaches 27.5 percent, and the vertical combustion reaches V-0 grade.
Comparative example 2
A preparation method of flame-retardant polyester fiber comprises the following steps:
the preparation method of the composite nano particle of the silica aerogel and the titanium dioxide comprises the following steps: adding the silica aerogel nano particles into deionized water, carrying out ultrasonic treatment for 9 minutes, removing the deionized water, carrying out quick freezing to obtain silica aerogel nano particles containing ice blocks, slowly dripping titanium tetrachloride into the silica aerogel nano particles containing the ice blocks, drying at 66 ℃ for 23 minutes, then placing the silica aerogel nano particles into a muffle furnace to be heated to 400 ℃, placing the silica aerogel nano particles into the muffle furnace to be heated to 200 ℃ according to the heating rate of 5 ℃ per minute, then heating to 400 ℃ from 200 ℃ according to the heating rate of 2 ℃ per minute, then placing the silica aerogel nano particles into liquid nitrogen to be quenched for 5-10 seconds, and taking out to obtain the composite nano particles of silica aerogel and titanium dioxide.
The preparation method of the fluorine-containing flame retardant comprises the following steps: 60mL of tetrahydrofuran was added to a three-necked flask, and hexachlorocyclotriphosphazene (0.04 mol) and sodium hydroxide (0.04 mol) were weighed and charged into the three-necked flask, followed by stirring until hexachlorocyclotriphosphazene was completely dissolved. Slowly dripping (0.04 mol of hydroxyl) hydroxyl fluorosilicone oil into a three-neck flask through a constant pressure dropping funnel, heating to 65 ℃, and reacting for 21 hours. Meanwhile, phenol (0.12 mol) is added into 40mL tetrahydrofuran, 5.52g of metallic sodium is weighed and put into the tetrahydrofuran solution of phenol in the form of fine chips, and the tetrahydrofuran solution of sodium phenolate is obtained after the sodium is completely disappeared. At normal temperature, a tetrahydrofuran solution of sodium phenolate was slowly dropped into the three-necked flask through a constant pressure dropping funnel. After the dropwise addition, slowly raising the temperature to 65 ℃, and continuing the reaction for 23 hours to obtain a milky white liquid. Removing tetrahydrofuran solvent by rotary evaporation, washing off impurities such as NaCl, sodium phenolate and the like by using deionized water, purifying by using trichloromethane, and carrying out rotary evaporation on a purified substance to obtain a tawny product, namely the fluorine-containing flame retardant.
The preparation method of the flame-retardant polyester master batch comprises the following steps: 9 parts of composite nano particles of silicon aerogel and titanium dioxide, the particle size of which is 200-700nm, and 23 parts of fluorine-containing flame retardant; 4 parts of trimethylolethane and 2.5 parts of phosphate coupling agent; 10100.6 parts of hindered phenol antioxidant; the rest is PET polyester granules; and then adding the mixture into a high-speed mixer with the rotating speed of 1200 r/min, mixing for 18 min at the mixing temperature of 160 ℃, adding the mixed materials into a double-screw extruder for melt blending, controlling the melting temperature at 280 ℃ and the rotating speed of the screws at 200 r/min, shearing and mixing for 13 min through the double-screw extruder, and then extruding, cooling, pelletizing, drying and packaging to obtain the flame-retardant polyester master batch.
And (3) carrying out melt blending spinning on 105 parts of PET polyester chips and 7 parts of flame-retardant polyester master batches by using a spinning assembly for spinning extrusion, cooling by circular air blowing, bundling and oiling, drafting, carrying out heat setting and winding to prepare the flame-retardant polyester fiber. The melt blending spinning temperature is 277 ℃, the air temperature of circular blowing is 28 ℃, and the air speed of the circular blowing is 0.4 m/min; the stretching ratio was 3.0 times, the stretching temperature was 154 ℃, the heat-setting temperature was 139 ℃ and the winding speed was 4200 m/min.
The limit oxygen index of the flame-retardant polyester fiber prepared by the invention reaches 30.2 percent, and the vertical combustion reaches V-0 grade.
The performance data of the polyester fiber prepared by the invention are tested according to the national standard, and are shown in fig. 7 and 8; it can be seen that the flame-retardant polyester fiber prepared by the invention has good toughness and antibacterial effect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the invention, and these modifications and decorations should also be regarded as the inventive content of the present invention.
Claims (10)
1. The flame-retardant polyester fiber is characterized by comprising the following raw materials in parts by weight: the flame-retardant polyester chip comprises 100-110 parts of polyester chips and 5-8 parts of flame-retardant polyester master batches; the flame-retardant polyester master batch comprises the following components: 8-10 parts of inorganic nanoparticles and 20-30 parts of flame retardant; 2-4 parts of a dispersing agent and 2-4 parts of a coupling agent; 0.2 to 1 part of antioxidant; the rest is polyester granules;
the polyester chip is a PET polyester chip; the polyester granules are PET polyester granules;
the flame retardant is a fluorine-containing flame retardant;
the inorganic nanoparticles contain silica aerogel nanoparticles.
2. The flame-retardant polyester fiber according to claim 1, wherein the coupling agent is a silicon coupling agent, a phosphate coupling agent or an aluminate coupling agent; the dispersing agent is polyethylene glycol, trimethylolethane or polyvinylpyrrolidone; the antioxidant is hindered phenol antioxidant 1010.
3. The flame-retardant polyester fiber according to claim 1, wherein the fluorine-containing flame retardant is prepared by the following steps: heating hexachlorocyclotriphosphazene, hydroxyl fluorosilicone oil and sodium hydroxide in tetrahydrofuran for reaction for a period of time, cooling to normal temperature, slowly adding a tetrahydrofuran solution of sodium phenolate, heating for reaction for a period of time, performing rotary evaporation to remove the tetrahydrofuran solvent, washing with water, washing with deionized water to remove NaCl and sodium phenolate impurities, purifying with trichloromethane, and performing rotary evaporation on the purified product to obtain a tawny product, namely the fluorine-containing flame retardant.
4. The flame-retardant polyester fiber according to claim 3, wherein the molar ratio of hexachlorocyclotriphosphazene, hydroxyfluorosilicone oil, sodium hydroxide and sodium phenolate is 1: 1: 1: 6-7; the reaction time is 20-24 hours.
5. The flame-retardant polyester fiber according to claim 1, wherein the inorganic nanoparticles are composite nanoparticles of silica aerogel and titanium dioxide.
6. The preparation method of the flame-retardant polyester fiber according to any one of claims 1 to 5, wherein the flame-retardant polyester fiber is prepared by the steps of spinning and extruding the polyester chips and the flame-retardant polyester master batches through a spinning assembly, cooling by circular blowing, bundling and oiling, drafting, heat setting and winding by a melt blending spinning method.
7. The method for preparing a flame-retardant polyester fiber according to claim 6, wherein the melt blending spinning temperature is 274 to 286 ℃, the circular blowing air temperature is 26 to 29 ℃, and the circular blowing air speed is 0.3 to 0.5 m/min; the stretching ratio is 2.7-3.5 times, the stretching temperature is 146-164 ℃, the heat setting temperature is 135-150 ℃, and the winding speed is 4000-4500 m/min.
8. The preparation method of the flame-retardant polyester fiber according to claim 6, wherein the preparation method of the flame-retardant polyester master batch comprises the following steps: the flame-retardant polyester master batch is prepared by mixing the components in proportion by weight, adding the mixture into a high-speed mixer with the rotating speed of 500-1500 rpm, mixing the mixture for 10-20 minutes at the mixing temperature of 140-180 ℃, adding the mixed material into a double-screw extruder for melt blending, controlling the melting temperature to be 270-290 ℃ and the rotating speed of screws to be 100-300 rpm, shearing and mixing the mixture for 10-15 minutes through the double-screw extruder, extruding, cooling, granulating, drying and packaging.
9. The preparation method of the flame-retardant polyester fiber as claimed in claim 6, wherein the preparation method of the composite nano-particles of the silicon aerogel and the titanium dioxide comprises the following steps: adding the silica aerogel nanoparticles into deionized water, performing ultrasonic treatment for 5-10 minutes, removing the deionized water, performing rapid freezing to obtain silica aerogel nanoparticles containing ice blocks, slowly dripping titanium tetrachloride into the silica aerogel nanoparticles containing ice blocks, drying at 60-70 ℃ for 20-30 minutes, and heating to 400 ℃ in a muffle furnace to obtain the composite nanoparticles of silica aerogel and titanium dioxide.
10. The method of claim 9, wherein the heating in the muffle furnace is performed at a temperature rate of 5 degrees per minute to 200 degrees, and then at a temperature rate of 2 degrees per minute from 200 degrees to 400 degrees.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114517407A (en) * | 2022-02-25 | 2022-05-20 | 江苏恒力化纤股份有限公司 | Preparation method of cyclic borate flame retardant and flame-retardant polyester fiber product thereof |
| WO2022245657A1 (en) * | 2021-05-18 | 2022-11-24 | Edwards Lifesciences Corporation | Implantable fibers, yarns and textiles |
| CN117210956A (en) * | 2023-09-04 | 2023-12-12 | 上海德福伦新材料科技有限公司 | Preparation method of flame-retardant melt-drip-inhibiting polyester fiber |
-
2021
- 2021-01-27 CN CN202110106807.3A patent/CN112663167A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022245657A1 (en) * | 2021-05-18 | 2022-11-24 | Edwards Lifesciences Corporation | Implantable fibers, yarns and textiles |
| CN114517407A (en) * | 2022-02-25 | 2022-05-20 | 江苏恒力化纤股份有限公司 | Preparation method of cyclic borate flame retardant and flame-retardant polyester fiber product thereof |
| CN114517407B (en) * | 2022-02-25 | 2023-08-29 | 江苏恒力化纤股份有限公司 | Cyclic borate flame retardant and preparation method of flame-retardant polyester fiber product thereof |
| CN117210956A (en) * | 2023-09-04 | 2023-12-12 | 上海德福伦新材料科技有限公司 | Preparation method of flame-retardant melt-drip-inhibiting polyester fiber |
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