阅读说明：本技术 一种氨纶纤维用螺环磷酸酯类阻燃剂的制备方法及基于其的阻燃氨纶纤维 (Preparation method of spiro phosphate flame retardant for spandex fiber and flame-retardant spandex fiber based on spiro phosphate flame retardant ) 是由 曾少华 汪启明 朱启免 柯许麟 陈鹏鹏 聂王焰 徐颖 周艺峰 于 2021-10-25 设计创作，主要内容包括：本发明公开了一种氨纶纤维用螺环磷酸酯类阻燃剂的制备方法及基于其的阻燃氨纶纤维,该制备方法为：先将大分子调节剂和季戊四醇搅拌均匀,再缓慢加入无水氯化铝,加热至80～120℃,再缓慢加入三氯氧磷,在80～120℃条件下反应2～7h,反应完成后冷却室温,调节阻燃剂pH＝7,100～150℃条件下减压蒸馏4～10h,得到透明粘稠液体,即为螺环磷酸酯类阻燃剂。本发明所得阻燃剂的阻燃效率高、有效防熔滴,能够满足氨纶纤维的高温熔融,且本发明的方法无废溶剂废气排放、生产工艺简单,成本可控。(The invention discloses a preparation method of a spiro phosphate flame retardant for spandex fibers and flame-retardant spandex fibers based on the spiro phosphate flame retardant, wherein the preparation method comprises the following steps: firstly, uniformly stirring a macromolecular regulator and pentaerythritol, slowly adding anhydrous aluminum chloride, heating to 80-120 ℃, slowly adding phosphorus oxychloride, reacting for 2-7 hours at 80-120 ℃, cooling to room temperature after the reaction is finished, adjusting the pH value of the flame retardant to 7, and distilling under reduced pressure for 4-10 hours at 100-150 ℃ to obtain transparent viscous liquid, namely the spiro phosphate flame retardant. The flame retardant obtained by the invention has high flame retardant efficiency, effectively prevents molten drops, can meet the requirement of high-temperature melting of spandex fibers, and has the advantages of no waste solvent and waste gas emission, simple production process and controllable cost.)

1. A preparation method of a spiro phosphate flame retardant for spandex fibers is characterized by comprising the following steps: firstly, uniformly stirring a macromolecular regulator and pentaerythritol, slowly adding anhydrous aluminum chloride, heating to 80-120 ℃, slowly adding phosphorus oxychloride, reacting for 2-7 hours at 80-120 ℃, cooling to room temperature after the reaction is finished, adjusting the pH value of the flame retardant to 7, and distilling under reduced pressure for 4-10 hours at 100-150 ℃ to obtain transparent viscous liquid, namely the spiro phosphate flame retardant.

2. The method of claim 1, wherein: the macromolecular regulator is one or a mixture of more of p-benzoquinone, phenol, hydroquinone and 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, and the mass ratio of the macromolecular regulator to the pentaerythritol is (1-10): 1.

3. the method of claim 1, wherein: the mass ratio of the phosphorus oxychloride to the total mass of the macromolecular regulator and the pentaerythritol is 0.1-10: 1.

4. the method of claim 1, wherein: the addition amount of the anhydrous aluminum chloride accounts for 0.05-5% of the total mass of the macromolecular regulator and the pentaerythritol.

5. The method of claim 1, wherein: the whole reaction process is carried out under the condition of stirring, and the stirring speed is 300-1000 r/min.

6. The method of claim 1, wherein: the adjustment of the flame retardant pH was carried out using a 10% by mass sodium hydroxide solution.

7. The method of claim 1, wherein the flame retardant is of high molecular weight and high temperature melt, suitable for flame retarding polyurethane spinning.

8. A spiro phosphate flame retardant for spandex fiber prepared by the preparation method of any one of claims 1 to 7.

9. A flame-retardant spandex fiber is characterized in that: adding the flame retardant of claim 8 into the polyurethane polymer solution, uniformly mixing, curing and spinning to obtain the flame-retardant spandex fiber.

Technical Field

The invention relates to the technical field of flame-retardant textile fibers, in particular to a preparation method of a spiro phosphate flame retardant for spandex fibers.

Background

The textile is an important basic material for the national civilization, and the application range of the textile covers a plurality of fields such as daily life, medical protection, aerospace, transportation and the like. In recent years, the ignition or combustion supporting of textiles brings great loss to the safety of life and property of people, and becomes a serious social problem. Scholars at home and abroad carry out a great deal of research work on flame retardance of fibers and textiles thereof. Polyurethane fiber (spandex for short) has the properties of high elasticity, high elongation and the like similar to rubber, and can be used for clothes which meet the requirement of comfort and need to have stretching elasticity, such as professional sportswear, fitness clothes, exercise clothes, protective clothes for surgical operation, performance clothes and the like. However, spandex has inflammability and high burning speed, and a candle wick effect is easily formed in the burning process, so that heat forms circulation, the fire intensity is enlarged immediately, and the spandex is difficult to extinguish. The development of flame-retardant spandex is receiving increasing attention.

Flame retardants are widely used to impart flame retardant properties to spandex fibers. However, conventional flame retardants tend to suffer from poor compatibility and spinning properties. At present, three methods for introducing a flame retardant into spandex fibers are mainly adopted: firstly, a fiber post-treatment method is adopted, but the method easily causes poor air permeability and moisture permeability, poor durability and the like of textiles, so that the application field of the textile is limited; and secondly, blending and adding a flame retardant, a dyeing assistant, other auxiliaries and the like into the polyurethane matrix, and then spinning to obtain the flame-retardant spandex. For example, patent CN201511003945.X reports a preparation method of a flame-retardant spandex fiber, the used flame retardant can endow spandex with anti-dripping property, but the flame-retardant effect is realized by mixing a compound flame retardant (a phenylphosphonate halogen-free phosphorus flame retardant/nonmetal oxide synergistic flame retardant) and a dyeing assistant in a polyurethane polymer solution for curing spinning, so that the flame-retardant efficiency is difficult to completely release; patent CN201610808145.3 reports a preparation method of zirconium phosphate synergistic flame-retardant spandex with uniform microdispersion, and the limit oxygen index LOI of the obtained flame-retardant spandex is more than 28. Thirdly, a reactive flame retardant is used, namely, a monomer containing a flame retardant component is subjected to polymerization reaction, so that spandex has a lasting flame retardant characteristic, but the flame retardant has the risk of influencing the physical performance of the spandex reaction process.

In recent years, cyclic or spiro-cyclic phosphate macromolecules are widely applied to polyurethane materials, and on the basis of meeting the lasting flame-retardant property of the polyurethane materials, the dispersity and the compatibility of the macromolecules in a polyurethane matrix can be improved, and the influence of a flame retardant on the fluidity of a polyurethane melt can be reduced. A large molecule of cyclic or spiro-cyclic phosphate suitable for preparing flame-retardant spandex fibers is reported at present, for example, Tanglinsheng and the like [ Tanglinsheng, Ligonin, catalytic synthesis of chlorinated spiro-phosphate [ J ]. fine chemical industry, 1999,16(2):49-50 ] synthesize chlorinated spiro-phosphate by taking phosphorus oxychloride and pentaerythritol as raw materials and aluminum chloride as a catalyst, but the flame retardant contains halogen elements and deviates from the requirements of current green halogen-free flame retardance. Patent CN201210054207.8 reports a reactive intumescent flame retardant for polyurethane, namely 3, 9-dichloro-2, 4,8, 10-tetraoxo-3, 9-diphosphospirane-3, 9-dioxy- [5,5] -undecane reacts with triethylamine to obtain a flame retardant integrating phosphorus, nitrogen and carbon, and the flame retardant has high flame retardant components of phosphorus and nitrogen and does not contain halogen. However, whether the flame retardant is suitable for flame-retarding spandex fibers has not been verified. In addition, the commonly used polytetrafluoroethylene anti-dripping agent has high cost and has the problem of uneven dispersion. Therefore, there is a need to develop spandex fiber and its textile with high flame retardancy, anti-dripping property, excellent spinnability and simple process.

Disclosure of Invention

The invention aims to provide a preparation method of a spiro phosphate flame retardant for spandex fibers, which has the advantages of high flame retardant efficiency for spandex, excellent spinnability, simple process, low production equipment investment, easily obtained raw materials, easiness in industrial production and capability of solving the difficulty in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of spiro phosphate flame retardant for spandex fiber is characterized in that: firstly, uniformly stirring a macromolecular regulator and pentaerythritol, slowly adding anhydrous aluminum chloride, heating to 80-120 ℃, slowly adding phosphorus oxychloride, reacting for 2-7 hours at 80-120 ℃, cooling to room temperature after the reaction is finished, adjusting the pH value of the flame retardant to 7, and distilling under reduced pressure for 4-10 hours at 100-150 ℃ to obtain transparent viscous liquid, namely the spiro phosphate flame retardant.

Further, the macromolecular regulator is one or a mixture of more of p-benzoquinone, phenol, hydroquinone and 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the mass ratio of the macromolecular regulator to the pentaerythritol is (1-10): 1.

further, the mass ratio of the phosphorus oxychloride to the total mass of the macromolecular regulator and the pentaerythritol is 0.1-10: 1.

Furthermore, the addition amount of the anhydrous aluminum chloride accounts for 0.05-5% of the total mass of the macromolecular regulator and the pentaerythritol.

Furthermore, the whole reaction process is carried out under the condition of stirring, and the stirring speed is 300-1000 r/min.

Further, the adjustment of the pH of the flame retardant was carried out using a 10% by mass sodium hydroxide solution.

Furthermore, the flame retardant has a high molecular weight and high-temperature melting structure, and is suitable for flame-retardant polyurethane spinning. And adding the flame retardant into the polyurethane polymer solution, uniformly mixing, curing and spinning to obtain the flame-retardant spandex fiber.

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

1. the spiro phosphate flame retardant is transparent viscous liquid, has a structure with a benzene ring (the structure is shown as below), is high in heat resistance, high in flame retardant efficiency, effective in molten drop prevention, capable of meeting the requirement of high-temperature melting of spandex fibers, good in spinnability of spandex, good in adaptability to pigments and wide in application field.

2. The spiro phosphate flame retardant is macromolecular, halogen-free and environment-friendly, does not precipitate in spandex, has a benzene ring structure which is easy to form carbon, and enables the spandex to be durable in flame retardance and excellent in water washing resistance.

3. The preparation of the flame retardant for polyurethane spinning has the advantages of no waste solvent and waste gas emission, no introduction of impurity elements, simple production equipment, low investment cost and suitability for industrial production.

Drawings

FIG. 1 is a thermogravimetric analysis test of the flame retardant prepared in example 1, with the test conditions: netzsch STA449F3A, air atmosphere, test temperature range room temperature to 700 ℃, heating rate 10 ℃/min.

FIG. 2 is an optical micrograph of spandex fiber prepared using the flame retardant of example 1.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.

Example 1

A stirrer, a thermometer and a condenser were installed in the dry reaction vessel. Firstly, uniformly stirring 54.1g of benzoquinone and 27.2g of pentaerythritol, adding 2.1g of anhydrous aluminum chloride, heating to 90 ℃, slowly adding 68.7g of phosphorus oxychloride, reacting for 5 hours at 90 ℃, cooling to room temperature after the reaction is finished, adjusting the pH value of the flame retardant to be 7 by using 10% sodium hydroxide, and distilling under reduced pressure for 8 hours at 150 ℃ to obtain transparent viscous liquid, namely the spiro phosphate flame retardant. The whole reaction process is carried out under stirring (speed 400 r/min).

Example 2

A stirrer, a thermometer and a condenser were installed in the dry reaction vessel. Firstly, 47.1g of phenol and 27.2g of pentaerythritol are uniformly stirred, 1.5g of anhydrous aluminum chloride is added, the mixture is heated to 90 ℃, 83.7g of phosphorus oxychloride is slowly added, the mixture reacts for 5 hours at 90 ℃, the room temperature is cooled after the reaction is finished, the pH value of the flame retardant is adjusted to 7 by using 10% sodium hydroxide, and the mixture is subjected to reduced pressure distillation for 8 hours at 150 ℃ to obtain transparent viscous liquid, namely the spiro phosphate flame retardant. The whole reaction process is carried out under stirring (speed 300 r/min).

Example 3

A stirrer, a thermometer and a condenser were installed in the dry reaction vessel. Firstly, uniformly stirring 55.2g of hydroquinone and 27.2g of pentaerythritol, adding 1.8g of anhydrous aluminum chloride, heating to 90 ℃, slowly adding 93.2g of phosphorus oxychloride, reacting for 5 hours at 90 ℃, cooling to room temperature after the reaction is finished, adjusting the pH value of the flame retardant to be 7 by using 10% sodium hydroxide, and distilling under reduced pressure for 8 hours at 150 ℃ to obtain transparent viscous liquid, namely the spiro phosphate flame retardant. The whole reaction process is carried out under stirring (speed 500 r/min).

Example 4

A stirrer, a thermometer and a condenser were installed in the dry reaction vessel. 162.3g of 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and 27.2g of pentaerythritol are uniformly stirred, 5.5g of anhydrous aluminum chloride is added, the mixture is heated to 90 ℃, 175.6g of phosphorus oxychloride is slowly added, the mixture reacts for 5 hours at the temperature of 90 ℃, the reaction product is cooled to room temperature after the reaction is finished, the pH value of the flame retardant is adjusted to 7 by using 10% sodium hydroxide, and the mixture is distilled under reduced pressure at the temperature of 150 ℃ for 8 hours to obtain transparent viscous liquid, namely the spiro phosphate flame retardant. The whole reaction process is carried out under stirring (speed of 700 r/min).

The flame retardant is suitable for polyurethane spinning, and the difference of macromolecular regulators can cause the difference of flame retardant properties of polyurethane fibers. Therefore, the present invention takes the flame retardant prepared in the above examples (examples 1 to 4) as an example, and applies it to spandex (whose main components are polyether glycol (PTMG) and 4, 4-diphenylmethane diisocyanate (MDI)). The flame retardant prepared in the above example, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole as an anti-ultraviolet agent, bis (N, N-dimethylhydrazide amino 4-phenyl) methane as an antioxidant, and sliced spandex were mixed uniformly in different proportions, and then extruded by a screw to granulate, and the manufactured particles were drawn by a spinning machine to obtain spandex fibers, and the flame retardant properties were tested, and some test results are shown in tables 1, 2, and 3:

table 1 flame retardant performance and smoke suppression performance data for the product of example 1 flame retardant spandex fiber

Table 2 flame retardant performance and smoke suppression performance data for the product of example 2 flame retardant spandex fiber

Table 3 flame retardant performance and smoke suppression performance data for the product of example 3 flame retardant spandex fiber

Table 4 flame retardant performance and smoke suppression performance data for the product of example 4 flame retardant spandex fiber

FIG. 1 is a thermogravimetric analysis test of the flame retardant prepared in example 1, with the test conditions: netzsch STA449F3A, air atmosphere, test temperature range room temperature to 700 ℃, heating rate 10 ℃/min. Fig. 2 is an optical micrograph of a spandex fiber prepared using the flame retardant of example 1, showing that the addition of 10 wt.% of flame retardant does not cause surface defects on the spandex fiber, compared to the pure sample (0 wt.% flame retardant content).

As can be seen from tables 1, 2, 3 and 4, the spirocyclic phosphate flame retardants of the present invention have excellent flame retardant and spinnability properties and better anti-dripping properties for polyurethanes. Meanwhile, the experiment also finds that the flame retardant has less damage to the mechanical property of the spandex fiber than the inorganic compound flame retardant, does not generate surface defects on the spandex fiber (see figure 2), and has excellent water washing resistance and lasting flame retardant property, so that the flame retardant can be used as an environment-friendly flame retardant.

The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.