阅读说明：本技术 阻燃聚酯纤维的制备方法 (Preparation method of flame-retardant polyester fiber ) 是由 黄金德 黄翔 于 2021-07-27 设计创作，主要内容包括：本发明公开了阻燃聚酯纤维的制备方法,以70-80份涤纶切片、22-28份阻燃母粒及2.0-5.0份抗熔滴剂混合加入螺杆挤出机熔融挤出,并将挤出的熔体通过纺丝组件纺丝成型,并辐照处理形成阻燃聚酯纤维,本方案中主要对阻燃母粒进行组分的调整并对应优化配方比例,通过植酸将锗螯合在多孔纳米颗粒的表面或孔腔内,并在高温中形成氧化锗,在燃烧过过程中,多组分协同配合,以氧化锗催化二乙基次磷酸铝形成小尺度陶瓷微球,继而与蒙脱土、硼酸锌以及二乙基次氯酸铝等阻燃剂配合,并且硼酸锌与二乙基次磷酸铝存在协同增效的作用,制备的聚酯纤维阻燃性能好,同时简化了制备工序,降低了成本。(The invention discloses a preparation method of flame-retardant polyester fiber, which comprises the steps of mixing 70-80 parts of polyester chips, 22-28 parts of flame-retardant master batches and 2.0-5.0 parts of anti-dropping agents, adding the mixture into a screw extruder for melt extrusion, spinning and forming the extruded melt through a spinning assembly, and performing irradiation treatment to form the flame-retardant polyester fiber, wherein the components of the flame-retardant master batches are adjusted, the formula proportion is correspondingly optimized, germanium is chelated on the surface or in the pore cavity of porous nano particles through phytic acid, germanium oxide is formed at high temperature, during the combustion process, the multi-component is cooperated, germanium oxide is used for catalyzing diethyl aluminum hypophosphite to form small-scale ceramic microspheres, and then the small-scale ceramic microspheres are cooperated with flame retardants such as montmorillonite, zinc borate, diethyl aluminum hypochlorite and the like, and the zinc borate and the diethyl aluminum hypophosphite have a synergistic effect, so that the prepared polyester fiber has good flame-retardant performance, meanwhile, the preparation process is simplified, and the cost is reduced.)

1. The preparation method of the flame-retardant polyester fiber is characterized in that 70-80 parts of polyester chips, 22-28 parts of flame-retardant master batches and 2.0-5.0 parts of anti-dropping agents are mixed and added into a screw extruder to be melted and extruded, the extruded melt is spun and formed through a spinning assembly, and the flame-retardant polyester fiber is formed through irradiation treatment;

the preparation method of the flame-retardant master batch comprises the following steps: mixing the porous nanoparticles prepared and molded by the phytic acid-soaked nano-scale sodium-based montmorillonite with sodium dodecyl benzene sulfonate, high-temperature resistant nano-zinc borate, germanium chloride, 3-aminopropyltriethoxysilane and a solvent, heating and stirring for 8-10h, and drying the obtained solid product at the temperature of 380-385 ℃ to form modified porous nanoparticles;

14-18 parts of modified porous nano particles, 3-5 parts of urea, 0.2-0.3 part of nano titanium dioxide, 2-3 parts of diethyl aluminum hypophosphite, 0.15-0.25 part of nano bamboo charcoal powder, 1.5-2.0 parts of antioxidant, 0.3-0.5 part of calcium stearate, 3-4 parts of ethylene bis fatty acid amide, 0.1-0.2 part of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and 65-75 parts of polyester chips are mixed and granulated to form the flame-retardant master batch.

2. The method for preparing a flame retardant polyester fiber according to claim 1, wherein: taking a proper amount of solvent, gradually adding sodium dodecyl benzene sulfonate accounting for 0.8-1.5% of the mass of the solvent, 15-18% of high-temperature-resistant nano zinc borate and 10-12% of germanium chloride, uniformly dispersing, adding porous nano particles of soaking phytic acid accounting for 8-12% of the mass of the solvent and 20-30% of 3-aminopropyl triethylsilane, uniformly dispersing, heating and stirring for 8-10h under the protection of inert gas, carrying out solid-liquid separation on the obtained reactant, and drying the separated solid at 385 ℃ of 380-.

3. The method for preparing a flame retardant polyester fiber according to claim 1, wherein: preparing high-temperature-resistant nano zinc borate: dissolving zinc nitrate hexahydrate in water in a container, heating to 60 ℃, adding borax decahydrate and zinc oxide in turn, reacting for 8-9h at 90-98 ℃, carrying out solid-liquid separation and drying to obtain the high-temperature-resistant nano zinc borate.

4. The method for preparing a flame retardant polyester fiber according to claim 1, wherein: the preparation of the porous nano-particles comprises the steps of adding nano-scale sodium-based montmorillonite and sodium bicarbonate into a water glass solution, heating to 55-65 ℃, adding a dilute hydrochloric acid solution after ultrasonic dispersion for 1-2h, and drying and grinding the obtained solid product to obtain the porous nano-material particles.

5. The method for preparing a flame retardant polyester fiber according to claim 1, wherein: the anti-dripping agent is triallyl isocyanurate.

6. The method for preparing a flame retardant polyester fiber according to claim 1, wherein: firstly, mixing the terylene slices with the flame-retardant master batch, adding an anti-dripping agent in the stirring process, and then adding the mixture into a screw extruder.

Technical Field

The invention relates to the technical field of fiber preparation, in particular to a preparation method of flame-retardant polyester fiber.

Background

Polyester fibers have been developed at a very high speed in recent years because of their excellent properties, and their applications have been becoming widespread. In order to meet the use requirements, some enterprises or research institutes continuously research and develop polyester fibers, especially for improving the flame retardant property, for example, a flame retardant fiber is disclosed in patent with application number CN2021102539488, the flame retardant property is improved by matching a composite flame retardant with a synergistic flame retardant, but the preparation process is complex, the cost is high, and the improvement is needed.

Disclosure of Invention

In order to solve at least one technical defect, the invention provides the following technical scheme:

the application document discloses a preparation method of flame-retardant polyester fiber, which comprises the steps of mixing 70-80 parts of polyester chips, 22-28 parts of flame-retardant master batches and 2.0-5.0 parts of anti-dropping agents, adding the mixture into a screw extruder for melt extrusion, carrying out spinning molding on the extruded melt through a spinning assembly, and carrying out irradiation treatment to form the flame-retardant polyester fiber;

the preparation method of the flame-retardant master batch comprises the following steps: mixing the porous nanoparticles prepared and molded by the phytic acid-soaked nano-scale sodium-based montmorillonite with sodium dodecyl benzene sulfonate, high-temperature resistant nano-zinc borate, germanium chloride, 3-aminopropyltriethoxysilane and a solvent, heating and stirring for 8-10h, and drying the obtained solid product at the high temperature of 330-345 ℃ to form modified porous nanoparticles;

14-18 parts of modified porous nano particles, 3-5 parts of urea, 0.2-0.3 part of nano titanium dioxide, 2-3 parts of diethyl aluminum hypophosphite, 0.15-0.25 part of nano bamboo charcoal powder, 1.5-2.0 parts of antioxidant, 0.3-0.5 part of calcium stearate, 3-4 parts of ethylene bis fatty acid amide, 0.1-0.2 part of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and 65-75 parts of polyester chips are mixed and granulated to form the flame-retardant master batch.

In the scheme, the components of the flame-retardant master batch are mainly adjusted and the formula proportion is optimized correspondingly, germanium is chelated on the surface or in the pore cavity of the porous nano particle through phytic acid, germanium oxide is formed at high temperature, in the combustion process, multiple components are cooperated, diethyl aluminum hypophosphite is catalyzed by the germanium oxide to form small-scale ceramic microspheres, and then the small-scale ceramic microspheres are cooperated with flame retardants such as montmorillonite, zinc borate and diethyl aluminum hypophosphite, and the zinc borate and the diethyl aluminum hypophosphite have a synergistic effect, so that the prepared polyester fiber is good in flame retardant property, the preparation process is simplified, and the cost is reduced.

Further, by weight, taking a proper amount of solvent, gradually adding sodium dodecyl benzene sulfonate accounting for 0.8-1.5% of the mass of the solvent, 15-18% of high-temperature-resistant nano zinc borate and 10-12% of germanium chloride, uniformly dispersing, adding porous nano particles of soaking phytic acid accounting for 8-12% of the mass of the solvent and 20-30% of 3-aminopropyl triethylsilane, uniformly dispersing, heating and stirring for 8-10h under the protection of inert gas, carrying out solid-liquid separation on obtained reactants, and drying the separated solid at 385 ℃ of 380-.

In the scheme, the porous nanoparticles are soaked in phytic acid in advance, then are mixed with germanium chloride and the like, germanium ions and the like are chelated on the surfaces of the pore cavities or the particles through a chelation effect, and then 3-aminopropyltriethoxysilane and hydroxyl radicals on the surfaces of the porous nanoparticles react to form bonds to form a three-dimensional network structure so as to fix components such as zinc borate and the like, so that the concentrated existence of various flame retardants is realized, and a synergistic effect is facilitated.

Further, preparing the high-temperature resistant nano zinc borate: dissolving zinc nitrate hexahydrate in water in a container, heating to 60 ℃, adding borax decahydrate and zinc oxide according to the temperature, maintaining the temperature at 90-98 ℃ for reaction for 8-9h, carrying out solid-liquid separation and drying to obtain high-temperature-resistant nano zinc borate, preparing the zinc borate by the components and the process, and finding that the decomposition temperature of the zinc borate is increased to 385 ℃ and is far higher than the decomposition temperature of the common zinc borate by thermogravimetric analysis and detection, wherein the reaction formula is as follows: 3.5Zn (NO)₃)₂·6H₂O+3.5NaB₄O₇·10H₂O+0.5ZnO＝2(2ZnO·3B₂O₃·3.5H₂O)+2H₃BO₃+7NaNO₃+46H₂O。

And further, preparing porous nano particles, namely adding nano-scale sodium-based montmorillonite and sodium bicarbonate into a water glass solution, heating to 55-65 ℃, ultrasonically dispersing for 1-2 hours, adding a dilute hydrochloric acid solution, and drying and grinding the obtained solid product to obtain the porous nano material particles.

Further, the anti-dripping agent is triallyl isocyanurate.

Further, mixing the terylene slices with the flame-retardant master batch, adding an anti-dropping agent in the stirring process, and then adding the mixture into a screw extruder.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention optimizes the components and proportion of the polyester fiber, greatly reduces the cost, simplifies the preparation process and has excellent flame retardant property.

Detailed Description

The present invention will be further described with reference to the following specific examples.

Example 1

Preparation of high-temperature-resistant zinc borate

Dissolving zinc nitrate hexahydrate in water in a container, heating to 60 ℃, adding borax decahydrate and zinc oxide according to the above reaction equation, reacting at 95 ℃ for 8h, filtering, washing and drying to obtain the high-temperature-resistant nano zinc borate.

Preparation of flame-retardant master batch

Firstly, preparing porous nano particles, namely adding nano sodium montmorillonite into a water glass solution with the mass being 8 times that of the nano sodium montmorillonite and the concentration being 15%, then adding sodium bicarbonate with the mass being 5% of the nano sodium montmorillonite, stirring for 80min, raising the temperature of the obtained mixed components to 55 ℃, ultrasonically dispersing for 1h, adding a dilute hydrochloric acid solution while stirring, naturally precipitating under the conditions that the pH is 4.8 and the temperature is 55 ℃, filtering the obtained mixture when no flocculent precipitate or bubbles are generated, drying the filtered product in vacuum to constant weight, and grinding to obtain the porous nano particles.

Secondly, adding the porous nano particles into an ethanol solution with the mass 4 times that of the porous nano particles, adding phytic acid with the same mass, soaking for 2 hours, and filtering.

Thirdly, adding 0.8 percent of sodium dodecyl benzene sulfonate, 15 percent of high temperature resistant nano zinc borate and 11 percent of germanium chloride into an ethanol solution, ultrasonically dispersing for 10min, adding 8 percent of freshly filtered porous nano particles and 20 percent of 3-aminopropyl triethylsilane into the ethanol solution, ultrasonically dispersing for 20min, heating to 60 ℃ under the protection of inert gas, stirring for 8h, filtering the obtained reactant, and drying the filtered solid in a muffle furnace at 380 ℃ for 5h to obtain the modified porous nano particles.

Fourthly, 14 parts of modified porous nano particles, 3 parts of urea, 0.2 part of nano titanium dioxide, 2 parts of aluminum diethylphosphinate, 0.15 part of nano bamboo charcoal powder, 1.5 parts of antioxidant B215, 0.3 part of calcium stearate, 3 parts of ethylene bis fatty acid amide, 0.1 part of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and 65 parts of polyester chips are mixed and added into a screw extruder to be melted and granulated to form the flame-retardant master batch.

Preparation of fibers

70 parts of polyester chips, 22 parts of flame-retardant master batches and 2 parts of anti-dropping agent (triallyl isocyanurate) are mixed and added into a screw extruder to be melted and extruded, the extruded melt is spun and formed through a spinning assembly, and is heat-set at 180 ℃, and then is irradiated on a high-energy electron accelerator, the irradiation dose is 100KGy, and the flame-retardant polyester fiber is formed after 25 min.

Example 2

Preparation of high temperature resistant Zinc borate

Preparation of flame-retardant master batch

First, porous nanoparticles were prepared as in example 1.

Second, the porous nanoparticles were soaked with phytic acid as in example 1.

Thirdly, adding 1.2 percent of sodium dodecyl benzene sulfonate, 17 percent of high temperature resistant nano zinc borate and 10 percent of germanium chloride into ethanol solution, ultrasonically dispersing for 10min, adding 10 percent of filtered porous nano particles and 25 percent of 3-aminopropyl triethylsilane into the ethanol solution, ultrasonically dispersing for 20min, heating to 60 ℃ under the protection of inert gas, stirring for 9h, filtering the obtained reactant, and drying the filtered solid in a muffle furnace at 382 ℃ for 5h to obtain the modified porous nano particles.

Fourthly, 16 parts of modified porous nano particles, 4 parts of urea, 0.25 part of nano titanium dioxide, 2.5 parts of diethyl aluminum hypophosphite, 0.2 part of nano bamboo charcoal powder, 1.7 parts of antioxidant B215, 0.4 part of calcium stearate, 3.5 parts of ethylene bis fatty acid amide, 0.15 part of isopropyl tris (dioctyl pyrophosphato acyloxy) titanate and 70 parts of polyester chips are mixed and added into a screw extruder to be melted and granulated to form the flame-retardant master batch.

Preparation of fibers

75 parts of polyester chips, 26 parts of flame-retardant master batches and 3.5 parts of anti-dropping agent (triallyl isocyanurate) are mixed and added into a screw extruder for melt extrusion, the extruded melt is spun and formed through a spinning assembly, and is heat-set at 180 ℃, and then the melt is irradiated on a high-energy electron accelerator, the irradiation dose is 100KGy, and the flame-retardant polyester fiber is formed after 25 min.

Example 3

Preparation of high temperature resistant Zinc borate

Preparation of flame-retardant master batch

First, porous nanoparticles were prepared as in example 1.

Second, the porous nanoparticles were soaked with phytic acid as in example 1.

Thirdly, adding 1.5 percent of sodium dodecyl benzene sulfonate, 18 percent of high temperature resistant nano zinc borate and 12 percent of germanium chloride into an ethanol solution, ultrasonically dispersing for 10min, adding 12 percent of filtered porous nano particles and 30 percent of 3-aminopropyl triethylsilane into the solvent, ultrasonically dispersing for 20min, heating to 60 ℃ under the protection of inert gas, stirring for 8h, filtering the obtained reactant, and drying the filtered solid in a muffle furnace at 384 ℃ for 5h to obtain the modified porous nano particles.

And fourthly, mixing 18 parts of modified porous nanoparticles, 5 parts of urea, 0.3 part of nano titanium dioxide, 3 parts of aluminum diethylphosphinate, 0.25 part of nano bamboo charcoal powder, 2.0 parts of antioxidant B215, 0.5 part of calcium stearate, 4 parts of ethylene bis fatty acid amide, 0.2 part of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and 75 parts of polyester chips, adding the mixture into a screw extruder, and carrying out melt granulation to form the flame-retardant master batch.

Preparation of fibers

Mixing 80 parts of polyester chips, 28 parts of flame-retardant master batches and 5 parts of anti-dripping agents (triallyl isocyanurate) and adding the mixture into a screw extruder for melt extrusion, spinning and forming the extruded melt through a spinning assembly, carrying out heat setting at 180 ℃, and then carrying out irradiation treatment on a high-energy electron accelerator, wherein the irradiation dose is 100KGy, and the flame-retardant polyester fiber is formed after 25 min.

Comparative example 1

The difference from example 3 is that the flame retardant masterbatch is free of germanium chloride.

Comparative example 2

The difference from example 3 is that no diethyl aluminum hypophosphite was present in the flame retardant masterbatch.

The flame-retardant fibers prepared in the above examples are tested, and as shown in the following table, the flame-retardant performance of the polyester fibers is excellent, and the tests are in accordance with GB/T8627-2007, GB/T2406.2-2009, GB/T8333-2008 and GB 20285-2006.

The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.