阅读说明：本技术 一种聚磷酸酯接枝石墨烯阻燃改性尼龙材料及制备方法 (Polyphosphate grafted graphene flame-retardant modified nylon material and preparation method thereof ) 是由 李红梅 王桂平 曾欢 于 2021-09-24 设计创作，主要内容包括：本发明涉及尼龙材料技术领域,且公开了一种聚磷酸酯接枝石墨烯阻燃改性尼龙材料,以三嗪基聚磷酸酯-修饰石墨烯作为复合阻燃剂,对尼龙6纤维进行改性,超支化含氮聚磷酸酯作为氮、磷协效阻燃剂,高温燃烧分解产生大量的氮气、氨气等不可燃气体,以及含氧磷酸衍生物,具有优异的抑烟性和促进成炭性,同时石墨烯在燃烧过程中形成连续的炭层,进一步抑制燃烧过程,从而显著增强尼龙材料的阻燃性能,并且通过调控复合阻燃剂的用量,对尼龙材料的力学强度的影响较小,使尼龙材料更好地应用在尼龙袋、包装用带等领域中。(The invention relates to the technical field of nylon materials, and discloses a polyphosphate ester grafted graphene flame-retardant modified nylon material, wherein triazine-based polyphosphate ester-modified graphene is used as a composite flame retardant to modify nylon 6 fibers, hyperbranched nitrogen-containing polyphosphate ester is used as a nitrogen and phosphorus synergistic flame retardant to generate a large amount of nitrogen, ammonia and other incombustible gases through high-temperature combustion decomposition, and an oxygen-containing phosphoric acid derivative.)

1. A polyphosphate grafted graphene flame-retardant modified nylon material is characterized in that: the preparation method of the polyphosphate grafted graphene flame-retardant modified nylon material comprises the following steps:

(1) triethylamine is used as an accelerant, and the benzene phosphoryl dichloride and the p-aminophenol are reacted to prepare the compound with the molecular formula of C₁₈H₁₇N₂O₃Bis (4-aminophenyl) phenylphosphonate of P;

(2) placing 1,3, 5-triazine-tricarboxylic acid in N, N-dimethylformamide solvent, adding oxalyl chloride, and performing acyl chlorination to obtain compound C₆O₃N₃Cl₃1,3, 5-triazine-triacyl chloride;

(3) adding a trichloromethane solvent and hydroxylated graphene into a reaction bottle, performing ultrasonic dispersion, adding 1,3, 5-triazine-triacyl chloride and reaction promoter pyridine, performing esterification reaction, performing reduced pressure distillation to remove the solvent, washing and precipitating by using trichloromethane and ethanol, and preparing acyl chloride triazine modified graphene;

(4) adding a trichloromethane solvent, acylchlorinated triazine modified graphene and an acid-binding agent triethylamine into a reaction bottle, performing ultrasonic homogenization, then adding 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate, performing in-situ hyperbranched polymerization, adding an N, N-dimethylformamide solvent for solvent, performing centrifugal separation to remove the solvent, and washing products by respectively using the N, N-dimethylformamide solvent, trichloromethane and ethanol to prepare triazine-based polyphosphate-modified graphene;

(5) the nylon 6 fiber and the triazine-based polyphosphate-modified graphene are subjected to melt blending, and high-speed melt spinning treatment is carried out at the temperature of 260-300 ℃ to prepare the polyphosphate grafted graphene flame-retardant modified nylon material.

2. The polyphosphate grafted graphene flame-retardant modified nylon material as claimed in claim 1, is characterized in that: in the step (3), the mass ratio of the hydroxylated graphene to the 1,3, 5-triazine-triacyl chloride to the reaction accelerator pyridine is 100:60-150: 25-60.

3. The polyphosphate grafted graphene flame-retardant modified nylon material as claimed in claim 1, is characterized in that: the esterification reaction in the step (3) is carried out at the temperature of 20-40 ℃ for 12-24 h.

4. The polyphosphate grafted graphene flame-retardant modified nylon material as claimed in claim 1, is characterized in that: in the step (4), the mass ratio of the acyl chloride triazine modified graphene to the acid-binding agent triethylamine to the 1,3, 5-triazine-triacyl chloride to the bis (4-aminophenyl) phenylphosphonate is 10:20-60:50-120: 65-160.

5. The polyphosphate grafted graphene flame-retardant modified nylon material as claimed in claim 1, is characterized in that: the temperature of the in-situ hyperbranched polymerization reaction in the step (4) is 20-50 ℃, and the reaction time is 20-40 h.

6. The polyphosphate grafted graphene flame-retardant modified nylon material as claimed in claim 1, is characterized in that: in the step (5), the mass ratio of the nylon 6 fiber to the triazine-based polyphosphate-modified graphene is 0.5-2: 100.

Technical Field

The invention relates to the technical field of nylon materials, in particular to a polyphosphate grafted graphene flame-retardant modified nylon material and a preparation method thereof.

Background

The nylon material is mainly polyamide polymer materials such as nylon 6 and the like, including aliphatic polyamide and aromatic polyamide, has excellent performances such as high temperature resistance, chemical corrosion resistance and mechanical strength, and has important application in the aspects of packaging materials, packing belts, food films and the like, but the traditional nylon material has poor flame retardance, so that the flame retardant modification of the nylon material becomes a research hotspot in recent years.

The graphene serving as an inorganic nano filler has important application in polymer materials such as nylon fibers, polyurethane and the like, the mechanical strength and the like of the materials are obviously improved, and a compact and continuous carbon layer can be formed by combustion, so that the graphene also has a wide application prospect in the flame retardant field.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a polyphosphate grafted graphene flame-retardant modified nylon material and a preparation method thereof, which have excellent flame-retardant property,

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a polyphosphate grafted graphene flame-retardant modified nylon material comprises the following steps:

(1) triethylamine is used as an accelerant, and the benzene phosphoryl dichloride and the p-aminophenol are reacted to prepare the compound with the molecular formula of C₁₈H₁₇N₂O₃Bis (4-aminophenyl) phenylphosphonate of P.

(2) Placing 1,3, 5-triazine-tricarboxylic acid in N, N-dimethylformamide solvent, adding oxalyl chloride, and performing acyl chlorination to obtain compound C₆O₃N₃Cl₃1,3, 5-triazine-triacyl chloride.

(3) Adding a trichloromethane solvent and hydroxylated graphene into a reaction bottle, performing ultrasonic dispersion, adding 1,3, 5-triazine-triacyl chloride and reaction promoter pyridine, performing esterification reaction, performing reduced pressure distillation to remove the solvent, washing and precipitating by using trichloromethane and ethanol, and thus obtaining the acylchlorinated triazine modified graphene.

(4) Adding a trichloromethane solvent, acylchlorinated triazine modified graphene and an acid-binding agent triethylamine into a reaction bottle, performing ultrasonic homogenization, then adding 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate, performing in-situ hyperbranched polymerization, adding an N, N-dimethylformamide solvent for solvent, performing centrifugal separation to remove the solvent, and washing the product with the N, N-dimethylformamide solvent, trichloromethane and ethanol respectively to obtain the triazinyl polyphosphate-modified graphene.

(5) The nylon 6 fiber and the triazine-based polyphosphate-modified graphene are subjected to melt blending, and high-speed melt spinning treatment is carried out at the temperature of 260-300 ℃ to prepare the polyphosphate grafted graphene flame-retardant modified nylon material.

Preferably, the mass ratio of the hydroxylated graphene, the 1,3, 5-triazine-triacyl chloride and the reaction promoter pyridine in the step (3) is 100:60-150: 25-60.

Preferably, the esterification reaction in the step (3) is carried out at the temperature of between 20 and 40 ℃ for 12 to 24 hours.

Preferably, in the step (4), the mass ratio of the acyl chloride triazine modified graphene to the acid-binding agent triethylamine to the 1,3, 5-triazine-triacyl chloride to the bis (4-aminophenyl) phenylphosphonate is 10:20-60:50-120: 65-160.

Preferably, the temperature of the in-situ hyperbranched polymerization reaction in the step (4) is 20-50 ℃, and the reaction time is 20-40 h.

Preferably, the mass ratio of the nylon 6 fibers to the triazine-based polyphosphate-modified graphene in the step (5) is 0.5-2: 100.

(III) advantageous technical effects

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

according to the polyphosphate grafted graphene flame-retardant modified nylon material, under the promotion action of pyridine, an acyl chloride functional group of 1,3, 5-triazine-triacyl chloride and a hydroxyl group of graphene are subjected to esterification reaction to obtain acyl chloride triazine modified graphene, the acyl chloride functional group is introduced to serve as an active polymerization site, in-situ hyperbranched polymerization reaction is carried out on the 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate on the surface of the graphene to obtain triazine-based polyphosphate-modified graphene, and hyperbranched nitrogen-containing polyphosphate containing a triazine ring unit and a phosphate ester unit is bonded and introduced into the graphene to realize organic functionalized modification of the graphene.

The polyphosphate grafted graphene flame-retardant modified nylon material takes triazine-based polyphosphate-modified graphene as a composite flame retardant to modify nylon 6 fibers, and hyperbranched nitrogen-containing polyphosphate as a nitrogen and phosphorus synergistic flame retardant to generate a large amount of nitrogen, ammonia and other incombustible gases through high-temperature combustion decomposition and an oxygen-containing phosphoric acid derivative, so that the material has excellent smoke suppression performance and carbon formation promotion performance, and simultaneously, the graphene forms a continuous carbon layer in the combustion process to further suppress the combustion process, thereby remarkably enhancing the flame retardant performance of the nylon material.

Drawings

Fig. 1 is a schematic of the reaction of hydroxylated graphene and 1,3, 5-triazine-triacyl chloride;

fig. 2 is a reaction scheme of acylchlorinated triazine modified graphene, 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: the preparation method of the polyphosphate grafted graphene flame-retardant modified nylon material comprises the following steps:

(1) triethylamine is used as an accelerant, and the benzene phosphoryl dichloride and the p-aminophenol are reacted to prepare the compound with the molecular formula of C₁₈H₁₇N₂O₃Bis (4-aminophenyl) phenylphosphonate of P.

(2) Placing 1,3, 5-triazine-tricarboxylic acid in N, N-dimethylformamide solvent, adding oxalyl chloride, and performing acyl chlorination to obtain compound C₆O₃N₃Cl₃1,3, 5-triazine-triacyl chloride.

(3) Adding a trichloromethane solvent and hydroxylated graphene into a reaction bottle, performing ultrasonic dispersion, adding 1,3, 5-triazine-triacyl chloride and reaction promoter pyridine at a mass ratio of 100:60-150:25-60, performing esterification reaction at 20-40 ℃ for 12-24h, performing reduced pressure distillation to remove the solvent, washing and precipitating by using trichloromethane and ethanol, and thus obtaining the acylchlorotriazine modified graphene.

(4) Adding a trichloromethane solvent, acylchlorinated triazine modified graphene and an acid-binding agent triethylamine into a reaction bottle, uniformly performing ultrasonic treatment, then adding 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate in a mass ratio of 10:20-60:50-120:65-160, performing in-situ hyperbranched polymerization at 20-50 ℃ for 20-40h, adding an N, N-dimethylformamide solvent for solvent, performing centrifugal separation to remove the solvent, and washing products with the N, N-dimethylformamide solvent, trichloromethane and ethanol respectively to obtain the triazinyl polyphosphate-modified graphene.

(5) And (2) melting and blending nylon 6 fibers and triazine-based polyphosphate-modified graphene in a mass ratio of 0.5-2:100, and performing high-speed melt spinning treatment at the temperature of 260-300 ℃ to obtain the polyphosphate grafted graphene flame-retardant modified nylon material.

Example 1

(1) Triethylamine is used as an accelerant, and the benzene phosphoryl dichloride and the p-aminophenol are reacted to prepare the compound with the molecular formula of C₁₈H₁₇N₂O₃Bis (4-aminophenyl) phenylphosphonate of P.

(2) Placing 1,3, 5-triazine-tricarboxylic acid in N, N-dimethylformamide solvent, adding oxalyl chloride, and performing acyl chlorination to obtain compound C₆O₃N₃Cl₃1,3, 5-triazine-triacyl chloride.

(3) Adding a trichloromethane solvent and hydroxylated graphene into a reaction bottle, performing ultrasonic dispersion, adding 1,3, 5-triazine-triacyl chloride and pyridine serving as a reaction promoter, performing esterification reaction at the temperature of 20 ℃ for 12 hours at the mass ratio of 100:60:25, performing reduced pressure distillation to remove the solvent, washing and precipitating by using trichloromethane and ethanol, and thus obtaining the acylchlorinated triazine modified graphene.

(4) Adding a trichloromethane solvent, acylchlorinated triazine modified graphene and an acid-binding agent triethylamine into a reaction bottle, uniformly performing ultrasonic treatment, then adding 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate in a mass ratio of 10:20:50:65, performing in-situ hyperbranched polymerization at 20 ℃ for 20h, adding an N, N-dimethylformamide solvent for solvent removal, performing centrifugal separation to remove the solvent, and washing the product by respectively using the N, N-dimethylformamide solvent, trichloromethane and ethanol to obtain the triazinyl polyphosphate-modified graphene.

(5) And (2) melting and blending nylon 6 fibers and triazine-based polyphosphate-modified graphene in a mass ratio of 0.5:100, and performing high-speed melt spinning treatment at 260 ℃ to obtain the polyphosphate grafted graphene flame-retardant modified nylon material.

Example 2

(1) Triethylamine is used as an accelerant, and the benzene phosphoryl dichloride and the p-aminophenol are reacted to prepare the compound with the molecular formula of C₁₈H₁₇N₂O₃Bis (4-aminophenyl) phenylphosphonate of P.

(2) Placing 1,3, 5-triazine-tricarboxylic acid in N, N-dimethylformamide solvent, adding oxalyl chloride, and performing acyl chlorination to obtain compound C₆O₃N₃Cl₃1,3, 5-triazine-triacyl chloride.

(3) Adding a trichloromethane solvent and hydroxylated graphene into a reaction bottle, performing ultrasonic dispersion, adding 1,3, 5-triazine-triacyl chloride and pyridine serving as a reaction promoter, performing esterification reaction at 40 ℃ for 12 hours at the mass ratio of 100:90:35, performing reduced pressure distillation to remove the solvent, washing and precipitating by using trichloromethane and ethanol, and thus obtaining the acylchlorinated triazine modified graphene.

(4) Adding a trichloromethane solvent, acylchlorinated triazine modified graphene and an acid-binding agent triethylamine into a reaction bottle, uniformly performing ultrasonic treatment, then adding 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate in a mass ratio of 10:32:70:90, performing in-situ hyperbranched polymerization at 30 ℃ for 24 hours, adding an N, N-dimethylformamide solvent for solvent removal, performing centrifugal separation to remove the solvent, and washing products by respectively using the N, N-dimethylformamide solvent, trichloromethane and ethanol to obtain the triazinyl polyphosphate-modified graphene.

(5) The method comprises the steps of melt blending nylon 6 fibers and triazine-based polyphosphate-modified graphene in a mass ratio of 1:100, and carrying out high-speed melt spinning treatment at 300 ℃ to obtain the polyphosphate grafted graphene flame-retardant modified nylon material.

Example 3

(1) Triethylamine is used as an accelerant, and the benzene phosphoryl dichloride and the p-aminophenol are reacted to prepare the compound with the molecular formula of C₁₈H₁₇N₂O₃Bis (4-aminophenyl) phenylphosphonate of P.

(2) Placing 1,3, 5-triazine-tricarboxylic acid in N, N-dimethylformamide solvent, adding oxalyl chloride, and performing acyl chlorination to obtain compound C₆O₃N₃Cl₃1,3, 5-triazine-triacyl chloride.

(3) Adding a trichloromethane solvent and hydroxylated graphene into a reaction bottle, performing ultrasonic dispersion, adding 1,3, 5-triazine-triacyl chloride and pyridine serving as a reaction promoter, performing esterification reaction at the temperature of 30 ℃ for 18 hours at the mass ratio of 100:120:48, performing reduced pressure distillation to remove the solvent, washing and precipitating by using trichloromethane and ethanol, and thus obtaining the acylchlorinated triazine modified graphene.

(4) Adding a trichloromethane solvent, acylchlorinated triazine modified graphene and an acid-binding agent triethylamine into a reaction bottle, uniformly performing ultrasonic treatment, then adding 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate in a mass ratio of 10:48:100:125, performing in-situ hyperbranched polymerization at 40 ℃ for 30h, adding an N, N-dimethylformamide solvent for solvent removal, performing centrifugal separation to remove the solvent, and washing products by respectively using the N, N-dimethylformamide solvent, trichloromethane and ethanol to obtain the triazinyl polyphosphate-modified graphene.

(5) And (2) melting and blending nylon 6 fibers and triazine-based polyphosphate-modified graphene in a mass ratio of 1.5:100, and performing high-speed melt spinning treatment at 280 ℃ to obtain the polyphosphate grafted graphene flame-retardant modified nylon material.

Example 4

(1) Triethylamine is used as an accelerant, and the benzene phosphoryl dichloride and the p-aminophenol are reacted to prepare the compound with the molecular formula of C₁₈H₁₇N₂O₃Bis (4-aminophenyl) phenylphosphonate of P.

(2) Placing 1,3, 5-triazine-tricarboxylic acid in N, N-dimethylformamide solvent, adding oxalyl chloride, and performing acyl chlorination to obtain compound C₆O₃N₃Cl₃1,3, 5-triazine-triacyl chloride.

(3) Adding a trichloromethane solvent and hydroxylated graphene into a reaction bottle, performing ultrasonic dispersion, adding 1,3, 5-triazine-triacyl chloride and pyridine serving as a reaction promoter, performing esterification reaction at 40 ℃ for 24 hours at a mass ratio of 100:150:60, performing reduced pressure distillation to remove the solvent, washing and precipitating by using trichloromethane and ethanol, and thus obtaining the acylchlorinated triazine modified graphene.

(4) Adding a trichloromethane solvent, acylchlorinated triazine modified graphene and an acid-binding agent triethylamine into a reaction bottle, uniformly performing ultrasonic treatment, then adding 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate in a mass ratio of 10:60:120:160, performing in-situ hyperbranched polymerization at 50 ℃ for 40h, adding an N, N-dimethylformamide solvent for solvent, performing centrifugal separation to remove the solvent, and washing products by respectively using the N, N-dimethylformamide solvent, trichloromethane and ethanol to obtain the triazinyl polyphosphate-modified graphene.

(5) And (2) melting and blending nylon 6 fibers and triazine-based polyphosphate-modified graphene in a mass ratio of 2:100, and performing high-speed melt spinning treatment at 300 ℃ to obtain the polyphosphate grafted graphene flame-retardant modified nylon material.

Comparative example 1

(1) Triethylamine is used as an accelerant, and the benzene phosphoryl dichloride and the p-aminophenol are reacted to prepare the compound with the molecular formula of C₁₈H₁₇N₂O₃Bis (4-aminophenyl) phenylphosphonate of P.

(2) Placing 1,3, 5-triazine-tricarboxylic acid in N, N-dimethylformamide solvent, adding oxalyl chloride, and performing acyl chlorination to obtain compound C₆O₃N₃Cl₃1,3, 5-triazine-triacyl chloride.

(3) Adding a trichloromethane solvent and hydroxylated graphene into a reaction bottle, performing ultrasonic dispersion, adding 1,3, 5-triazine-triacyl chloride and pyridine serving as a reaction promoter, performing esterification reaction at 40 ℃ for 18h at the mass ratio of 100:30:12, performing reduced pressure distillation to remove the solvent, washing and precipitating by using trichloromethane and ethanol, and thus obtaining the acylchlorinated triazine modified graphene.

(4) Adding a trichloromethane solvent, acylchlorinated triazine modified graphene and an acid-binding agent triethylamine into a reaction bottle, uniformly performing ultrasonic treatment, then adding 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate in a mass ratio of 10:8:25:35, performing in-situ hyperbranched polymerization at 30 ℃ for 30h, adding an N, N-dimethylformamide solvent for solvent, performing centrifugal separation to remove the solvent, and washing products by respectively using the N, N-dimethylformamide solvent, trichloromethane and ethanol to obtain the triazinyl polyphosphate-modified graphene.

(5) And (2) melting and blending nylon 6 fibers and triazine-based polyphosphate-modified graphene in a mass ratio of 0.2:100, and performing high-speed melt spinning treatment at 280 ℃ to obtain the polyphosphate grafted graphene flame-retardant modified nylon material.

Comparative example 2

(1) Triethylamine is used as an accelerant, and the benzene phosphoryl dichloride and the p-aminophenol are reacted to prepare the compound with the molecular formula of C₁₈H₁₇N₂O₃Bis (4-aminophenyl) phenylphosphonate of P.

(2) Placing 1,3, 5-triazine-tricarboxylic acid in N, N-dimethylformamide solvent, adding oxalyl chloride, and performing acyl chlorination to obtain compound C₆O₃N₃Cl₃1,3, 5-triazine-triacyl chloride.

(3) Adding a trichloromethane solvent and hydroxylated graphene into a reaction bottle, performing ultrasonic dispersion, adding 1,3, 5-triazine-triacyl chloride and pyridine serving as a reaction promoter, performing esterification reaction at 40 ℃ for 24 hours at the mass ratio of 100:180:75, performing reduced pressure distillation to remove the solvent, washing and precipitating by using trichloromethane and ethanol, and thus obtaining the acylchlorinated triazine modified graphene.

(4) Adding a trichloromethane solvent, acylchlorinated triazine modified graphene and an acid-binding agent triethylamine into a reaction bottle, uniformly performing ultrasonic treatment, then adding 1,3, 5-triazine-triacyl chloride and bis (4-aminophenyl) phenylphosphonate in a mass ratio of 10:75:145:190, performing in-situ hyperbranched polymerization at 50 ℃ for 20h, adding an N, N-dimethylformamide solvent for solvent removal, performing centrifugal separation to remove the solvent, and washing products by respectively using the N, N-dimethylformamide solvent, trichloromethane and ethanol to obtain the triazinyl polyphosphate-modified graphene.

(5) And (2) melting and blending nylon 6 fibers and triazine-based polyphosphate-modified graphene in a mass ratio of 2.5:100, and performing high-speed melt spinning treatment at 300 ℃ to obtain the polyphosphate grafted graphene flame-retardant modified nylon material.

The UL94 fire rating of the polyphosphate grafted graphene flame-retardant modified nylon material was tested using an RF2186 vertical flammability tester.

And testing the tensile property and the bending strength of the modified nylon material by using an HY-2010 tensile testing machine.