阅读说明：本技术 一种新型三嗪衍生物阻燃剂的合成及应用 (Synthesis and application of novel triazine derivative flame retardant ) 是由 邓继勇 符雅芬 颜东 周鄂 潘紫璐 姜亚宁 于 2019-10-09 设计创作，主要内容包括：本发明公开一种基于三嗪六元杂环和磷杂菲结构的新型三嗪衍生物阻燃剂(NPFR)的合成及其在棉织纺织品上的应用,其化学结构名称为三-[4-(对羟基苯胺-磷杂菲)亚甲基-苯氧基]-1,3,5-三嗪,简称为NPFR。其制备方法为：由三聚氯氰(TCT)和对羟基苯甲醛反应合成2,4,6-三(4-醛基苯氧基)-1,3,5-三嗪(ZJT)；再由ZJT、对氨基苯酚和9,10-二氢-9-氧杂-10-膦菲-10-氧化物(DOPO)反应合成NPFR。本发明选用具有优良热稳定性能的三嗪六元杂环(N源)为核,通过引入良好阻燃性能的DOPO基团(P源),即提升了阻燃剂分子的热稳定性能,又通过N-P协效作用提高了阻燃性能。本发明的新型三嗪衍生物阻燃剂NPFR应用于棉织物阻燃时,具有较高的极限氧指数和优良的成炭率。(The invention discloses a synthesis method of a novel triazine derivative flame retardant (NPFR) based on a triazine six-membered heterocyclic ring and a phosphaphenanthrene structure and application of the flame retardant (NPFR) in cotton textiles, wherein the chemical structure of the flame retardant is tris- [4- (p-hydroxyphenylamine-phosphaphenanthrene) methylene-phenoxy ] -1, 3, 5-triazine, namely NPFR for short. The preparation method comprises the following steps: cyanuric chloride (TCT) and p-hydroxybenzaldehyde are reacted to synthesize 2, 4, 6-tri (4-aldehyde phenoxy) -1, 3, 5-triazine (ZJT); then, ZJT, p-aminophenol and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) react to synthesize NPFR. According to the invention, triazine hexa-heterocyclic ring (N source) with excellent thermal stability is selected as a core, and through introducing DOPO group (P source) with excellent flame retardant property, the thermal stability of flame retardant molecules is improved, and the flame retardant property is improved through N-P synergistic effect. When the novel triazine derivative flame retardant NPFR is applied to cotton fabric flame retardance, the flame retardant NPFR has higher limit oxygen index and excellent char yield.)

1. A novel triazine derivative flame-retardant material is characterized by having a structural formula as follows:

the chemical structure name of the triazine derivative is tris- [4- (p-hydroxyphenylamine-phosphaphenanthrene) methylene-phenoxy ] -1, 3, 5-triazine, and the name is simply called as follows: NPFR.

2. A process for the preparation of a novel triazine derivative flame retardant material according to claim 1, characterized in that it comprises the following steps:

(1) cyanuric chloride (TCT) is taken as a core and reacts with p-hydroxybenzaldehyde (4-HBA) to prepare 2, 4, 6-tri (4-aldehyde phenoxy) -1, 3, 5-triazine (ZJT);

(2) the triazine derivative flame retardant material NPFR as claimed in claim 1 is prepared by reacting 2, 4, 6-tris (4-formylphenoxy) -1, 3, 5-triazine (ZJI) with p-aminophenol (PAP), DOPO.

3. The process for preparing a novel triazine derivative flame retardant material according to claim 2, wherein: in the step (1), the molar ratio of the raw materials TCT to 4-HBA is 1 to 2.4-3.6.

4. The process for preparing a novel triazine derivative flame retardant material according to claim 2, wherein: in the step (2), the raw material molar ratio ZJT, DOPO and PAP is 1: 2.4-3.6.

5. The process for preparing a novel triazine derivative flame retardant material according to claim 2, wherein: in the step (1), triethylamine is selected as a phase transfer catalyst (TEA), and the dosage of the phase transfer catalyst is 0.1-0.4: 1 when the molar ratio of TEA to 4-HBA is equal to.

6. The process for preparing a novel triazine derivative flame retardant material according to claim 2, wherein: in the step (1), adding a sodium hydroxide solution, wherein the molar ratio of the sodium hydroxide to the TCT to the NaOH is 1: 1; the dropping temperature of the NaOH solution is selected to be 5-10 ℃, and the reflux temperature is selected to be the final reaction temperature.

7. The process for preparing a novel triazine derivative flame retardant material according to claim 2, wherein: in the step (1), the reaction time is 0.5-2.5 hours.

8. The process for preparing a novel triazine derivative flame retardant material according to claim 2, wherein: and (3) carrying out the reaction in the step (2), namely, after the 1, 4-dioxane solution of the p-aminophenol (PAP) is added dropwise and subjected to reflux reaction for about 12 hours, adding the 1, 4-dioxane solution of the DOPO and then refluxing for about 12 hours.

9. The process for preparing a novel triazine derivative flame retardant material according to claim 2, wherein: in the step (2), the reaction atmosphere is selected from a nitrogen atmosphere.

10. Process for the preparation of novel triazine derivative flame retardant materials according to any of claims 2 to 9, characterized in that: the reaction in the step (1) is specifically as follows:

synthesis of 2, 4, 6-tris (4-formylphenoxy) -1, 3, 5-triazine (ZJT)

Weighing a certain amount of p-hydroxybenzaldehyde and cyanuric chloride in a 250mL beaker, adding dichloromethane for dissolution, carrying out ice-water bath at 0-5 ℃, stirring, and adding Triethylamine (TEA) as a phase transfer catalyst; weighing a corresponding amount of sodium hydroxide and dissolving the sodium hydroxide in distilled water; then slowly adding sodium hydroxide solution, and stirring for 10 minutes to ensure that the reaction is complete; introducing the reactants into a 500mL three-neck flask, and heating and refluxing for two hours; then evaporating dichloromethane, filtering, drying and recrystallizing ethyl acetate; obtaining an organic intermediate 2, 4, 6-tri (4-aldehyde phenoxy) -1, 3, 5-triazine (ZJT);

the reaction in the step (2) is specifically as follows:

synthesis of target triazine derivative flame-retardant molecule NPFR

Weighing a certain amount of ZJT, dissolving the ZJT in a three-neck flask filled with 1, 4-dioxane, stirring the mixture until the ZJT is dissolved under the protection of nitrogen, weighing a corresponding molar amount of p-aminophenol, dissolving the p-aminophenol in the 1, 4-dioxane, dropwise adding the p-aminophenol into the three-neck flask, heating the mixture to 102 ℃, carrying out reflux reaction for about 12 hours, adding a corresponding molar amount of DOPO, continuously refluxing for about 12 hours, carrying out suction filtration while the mixture is hot, concentrating the filtrate by using a rotary evaporator, pouring the concentrated filtrate into cold ethanol, stirring the mixture until white precipitate is separated out, carrying out suction filtration, washing, and carrying out vacuum drying at 65 ℃ overnight to obtain the target triazine derivative flame: NPFR;

11. use of the triazine derivative flame retardant molecule NPFR of claim 1 in textile substrates to be flame retarded; the textile type substrate to be flame-retarded is preferably a cotton textile.

Technical Field

The invention relates to the technical field of flame retardant material preparation, in particular to preparation of a novel triazine derivative flame retardant material based on cyanuric chloride and DOPO structures and application of the flame retardant material in various flame-retardant base materials, especially application in cotton textiles.

Background

With the widespread use of polymers, fire safety is becoming an increasing concern. Many safety testing organizations, including the Underwriters Laboratories (UL), the international organization for standardization (ISO), and the American Society for Testing and Materials (ASTM), have promulgated various types of standard standards that define the flame retardant properties required of a polymer in a given classification.

Most commercial textiles are too inflammable, cotton fibers are one of the most common textile raw materials, the limited oxygen index of the cotton fibers is only 18%, the cotton fibers are extremely easy to burn, and cause fire hazard to human life and property safety, so the cotton fibers are required to be subjected to flame retardant finishing to improve the flame resistance of the cotton fibers.

In order to obtain a high-efficiency, environment-friendly and green textile flame-retardant material, the novel triazine derivative flame-retardant material is invented, and the novel triazine derivative flame-retardant material has the structural characteristics that: (1) taking a triazine six-membered heterocyclic structure with excellent thermal stability as a basic skeleton, and grafting a DOPO structure into the triazine skeleton through nucleophilic substitution reaction; (2) triazine ring in the molecular structure contains abundant N source, and DOPO group contains P source. According to the characteristics of molecular structures, the material is a novel triazine derivative flame retardant with excellent performance, can endow a flame-retardant substrate with good flame retardant performance, and is expected to have excellent application prospects in the fields of textile industry, plastics, leather and the like.

Disclosure of Invention

The invention aims to provide a novel environment-friendly and efficient triazine derivative flame-retardant material and a preparation method thereof.

The technical scheme of the invention is as follows:

a triazine derivative flame-retardant material has a molecular structure shown as follows:

the chemical structure name of the triazine derivative is tris- [4- (p-hydroxyphenylamine-phosphaphenanthrene) methylene-phenoxy ] -1, 3, 5-triazine, and the name is simply called as follows: NPFR.

The preparation method of the novel triazine derivative flame retardant material takes triazine six-membered heterocyclic ring as a basic skeleton, introduces structures such as DOPO and the like into the triazine skeleton through nucleophilic substitution reaction, and comprises the following steps:

(1) using dichloromethane as solvent, reacting TCT with 4-HBA to obtain 2, 4, 6-tri (4-aldehyde phenoxy) -1, 3, 5-triazine (ZJT).

(2) Under the nitrogen atmosphere, DOPO and PAP are introduced into a ZJT structure to obtain the novel triazine derivative flame-retardant molecule NPFR.

Further, in the step (1), the molar ratio of the raw materials TCT to 4-HBA is 1: 2.4-3.6.

Further, in the step (2), the molar ratio ZJT, DOPO and PAP is 1: 2.4-3.6.

Furthermore, in the step (1), triethylamine is selected as a catalyst (TEA), and the dosage of the catalyst is TEA: 4-HBA which is 0.1-0.4: 1.

Further, in the step (1), the dripping temperature of the NAOH solution is selected to be 5-10 ℃, and the reflux temperature is selected to be the final reaction temperature. .

Further, in the step (1), the reaction time is 0.5 to 2.5 hours

Further, in the step (2), the 1, 4-dioxane solution of p-aminophenol is dripped and then subjected to reflux reaction for about 12 hours, and the 1, 4-dioxane solution of DOPO is added and then subjected to reflux reaction for about 12 hours.

Further, in the step (2), the reaction environment is a nitrogen atmosphere.

Further, the reaction of the step (1) is specifically as follows:

synthesis of 2, 4, 6-tris (4-formylphenoxy) -1, 3, 5-triazine (ZJT)

Weighing a certain amount of p-hydroxybenzaldehyde and cyanuric chloride in a 250mL beaker, adding dichloromethane for dissolution, carrying out ice-water bath at 0-5 ℃, stirring, and adding Triethylamine (TEA) as a phase transfer catalyst. The corresponding amount of sodium hydroxide was weighed and dissolved in distilled water. The sodium hydroxide solution was then added slowly and stirred for 1O min to complete the reaction. The reaction mixture was introduced into a 500mL three-necked flask and heated under reflux for two hours. Then the dichloromethane is distilled off, filtered, dried and recrystallized by ethyl acetate. To obtain the organic intermediate 2, 4, 6-tri (4-aldehyde phenoxy) -1, 3, 5-triazine (ZJT).

The reaction in the step (2) is specifically as follows:

synthesis of novel triazine derivative flame-retardant molecule NPFR

Weighing a certain amount of ZJT, dissolving the ZJT in a three-neck flask filled with 1, 4-dioxane, stirring the mixture until the ZJT is dissolved under the protection of nitrogen, weighing a corresponding molar amount of p-aminophenol, dissolving the p-aminophenol in the 1, 4-dioxane, dropwise adding the p-aminophenol into the three-neck flask, heating the mixture to 102 ℃, carrying out reflux reaction for about 12 hours, adding a corresponding molar amount of DOPO, continuously refluxing for about 12 hours, carrying out suction filtration while the mixture is hot, concentrating the filtrate by using a rotary evaporator, pouring the concentrated filtrate into cold ethanol, stirring the mixture until white precipitate is separated out, carrying out suction filtration, washing, and carrying out vacuum drying at 65 ℃ overnight to obtain the target triazine derivative flame: NPFR.

The invention also aims to apply the triazine derivative-based flame-retardant material to the flame retardance of various flame-retardant base materials, particularly cotton fabrics, so as to endow the flame-retardant base materials with green and efficient flame-retardant properties.

Taking the flame retardant application of the novel triazine derivative flame retardant material in cotton fabric as an example, the invention has the beneficial effects that:

(1) the invention takes TCT, 4-HBA, DOPO and PAP as raw materials to synthesize a novel environment-friendly and high-efficiency triazine derivative flame-retardant material: NPFR, which compound is not reported in the prior art.

(2) DSC and TG tests show that the novel triazine derivative flame retardant material has good thermal property and char forming property, and can endow a flame-retardant base material with good flame retardant property.

(3) By taking the flame retardant finishing of cotton fabrics as an example, performance tests such as limit oxygen index, vertical combustion experiments and the like show that the novel triazine derivative flame retardant material disclosed by the invention endows the cotton fabrics with excellent flame retardant performance and can play an outstanding flame retardant effect at high temperature.

Drawings

FIG. 1 is a DSC and TG analysis test curve of NPFR obtained in example 2 of the present invention.

FIG. 2 is a TG and TGA curve of cotton fabric before and after flame retardant finishing in example 2 of the present invention.

FIG. 3 is an IR spectrum of NPFR obtained in example 2 of the present invention.

FIG. 4 is a nuclear magnetic hydrogen spectrum of ZJT obtained in example 1 of the present invention.

FIG. 5 is a nuclear magnetic hydrogen spectrum of NPFR obtained in example 3 of the present invention.

FIG. 6 is a comparison diagram of the state of the cotton fabric after combustion before and after finishing by the novel triazine derivative flame retardant material.

FIG. 7 is a scanning electron microscope image of cotton fabric before and after finishing by the novel triazine derivative flame retardant material.

Detailed Description

The present invention is further illustrated in detail below with reference to specific examples, which are not intended to limit the scope of the invention in any way.