Flame retardant containing DOPS/phosphazene structure as well as preparation method and application thereof

Abstract

The invention provides a flame retardant containing a DOPS / phosphazene structure as well as a preparation method and application thereof, and relates to the technical field of flame-retardant materials. According to the flame retardant containing the DOPS / phosphazene structure, a phosphazene group and DOPS are introduced into the same flame retardant molecule through molecular design, and a flame retardant material with excellent performance can be obtained through the synergistic effect of bifunctional groups. The DOPS can enhance the flame-retardant effect of phosphorus and promote dehydration and charring of a base material, so that the DOPS can also show excellent flame-retardant performance in a condensed phase; cyclotriphosphazene has a six-membered ring structure with a basic framework formed by alternately arranging phosphorus and nitrogen elements, and six chlorine atoms on a phosphazene ring have active chemical reactivity and can be completely or partially substituted by a DOPS substituent group shown in the structural formula (I); and then the flame retardant efficiency of phosphaphenanthrene is improved by utilizing the high char forming performance of phosphazene, and the synergistic flame-retardant effect is achieved.

Description

technical field

[0001] The invention relates to the technical field of flame retardant materials, in particular to a flame retardant containing DOPS / phosphazene structure and its preparation method and application. Background technique

[0002] At present, halogen-containing flame retardants will emit toxic and corrosive gases and smoke when they are burned or processed at high temperature, causing environmental pollution and endangering human health. As people's requirements for environmental quality of life are getting higher and higher, and various national environmental protection documents have been issued one after another, therefore, the trend of polymer flame retardant materials will be halogen-free.

[0003] Among the numerous halogen-free flame retardants, phosphophenanthrene flame retardants have been widely studied because of their environmental friendliness, high carbon content, good compatibility, and long-lasting flame retardancy. Utilizing the active charact...

Examples

preparation example Construction

[0057] According to one aspect of the present invention, a kind of preparation method of above-mentioned flame retardant containing DOPS / phosphazene structure, described preparation method comprises the following steps:

[0058] (a) Using hexachlorocyclotriphosphazene and 4-hydroxybenzaldehyde and optional phenol as raw materials, add an acid-binding agent to carry out a nucleophilic substitution reaction in a substitution reaction solvent, followed by filtration, distillation, washing and drying , to obtain a cyclotriphosphazene compound containing an aldehyde group;

[0059] (b) carry out addition reaction with the cyclotriphosphazene compound and DOPS containing the aldehyde group that step (a) makes in the addition reaction solvent, wash, filter and dry successively subsequently, obtain the compound containing DOPS / phosphazene structure flame retardant.

[0060] The preparation method of the flame retardant containing DOPS / phosphazene structure provided by the present inv...

Embodiment 1

[0081] A kind of flame retardant containing DOPS / phosphazene structure, the preparation method of the described flame retardant containing DOPS / phosphazene structure comprises the following steps:

[0082] (a) Preparation of HAP

[0083] 1. HCCP and 4-hydroxybenzaldehyde are weighed according to the molar ratio of 1:7;

[0084] 2. Use the organic solvent tetrahydrofuran as the reaction medium, so that the reactants can fully react;

[0085] 3. Add the weighed 4-hydroxybenzaldehyde into a three-necked flask equipped with a thermometer, condenser, and stirrer, add an appropriate amount of solvent and acid-binding agent triethylamine, install a reflux condensation device, and raise the temperature to 60°C. Then add an appropriate amount of solvent to the weighed HCCP, and after it is completely dissolved, add it dropwise to the above reaction system within 1 hour. After the addition is complete, raise the temperature to 65°C and continue the reflux reaction for 20 hours;

[008...

Embodiment 2

[0099] A kind of flame retardant containing DOPS / phosphazene structure, the preparation method of the described flame retardant containing DOPS / phosphazene structure comprises the following steps:

[0100] (a) Preparation of HAP

[0101] 1. HCCP and 4-hydroxybenzaldehyde are weighed according to the molar ratio of 1:6;

[0102] 2,3, with embodiment 1;

[0103] Finally, the product HAP was obtained as a white powdery solid with a melting point of 156.3-157.4° C., a yield of 97.2%, and a purity of >99.0%.

[0104] (b) Preparation of HAP-DOPS

[0105] 1. Weigh DOPS and HAP according to the molar ratio of 8:1;

[0106] 2. Use the mixed solution of organic solvent chlorobenzene and ethanol as the reaction medium, so that the reactants can fully react;

[0107] 3. Add the weighed DOPS into a four-necked flask equipped with a thermometer, condenser tube, stirrer and protective gas inlet and outlet, add an appropriate amount of solvent and triethylamine, install a reflux condensat...

technical field

[0001] The invention relates to the technical field of flame retardant materials, in particular to a flame retardant containing DOPS / phosphazene structure and its preparation method and application. Background technique

[0002] At present, halogen-containing flame retardants will emit toxic and corrosive gases and smoke when they are burned or processed at high temperature, causing environmental pollution and endangering human health. As people's requirements for environmental quality of life are getting higher and higher, and various national environmental protection documents have been issued one after another, therefore, the trend of polymer flame retardant materials will be halogen-free.

[0003] Among the numerous halogen-free flame retardants, phosphophenanthrene flame retardants have been widely studied because of their environmental friendliness, high carbon content, good compatibility, and long-lasting flame retardancy. Utilizing the active charact...

Examples

preparation example Construction

[0057] According to one aspect of the present invention, a kind of preparation method of above-mentioned flame retardant containing DOPS / phosphazene structure, described preparation method comprises the following steps:

[0058] (a) Using hexachlorocyclotriphosphazene and 4-hydroxybenzaldehyde and optional phenol as raw materials, add an acid-binding agent to carry out a nucleophilic substitution reaction in a substitution reaction solvent, followed by filtration, distillation, washing and drying , to obtain a cyclotriphosphazene compound containing an aldehyde group;

[0059] (b) carry out addition reaction with the cyclotriphosphazene compound and DOPS containing the aldehyde group that step (a) makes in the addition reaction solvent, wash, filter and dry successively subsequently, obtain the compound containing DOPS / phosphazene structure flame retardant.

[0060] The preparation method of the flame retardant containing DOPS / phosphazene structure provided by the present inv...

Embodiment 1

[0081] A kind of flame retardant containing DOPS / phosphazene structure, the preparation method of the described flame retardant containing DOPS / phosphazene structure comprises the following steps:

[0082] (a) Preparation of HAP

[0083] 1. HCCP and 4-hydroxybenzaldehyde are weighed according to the molar ratio of 1:7;

[0084] 2. Use the organic solvent tetrahydrofuran as the reaction medium, so that the reactants can fully react;

[0085] 3. Add the weighed 4-hydroxybenzaldehyde into a three-necked flask equipped with a thermometer, condenser, and stirrer, add an appropriate amount of solvent and acid-binding agent triethylamine, install a reflux condensation device, and raise the temperature to 60°C. Then add an appropriate amount of solvent to the weighed HCCP, and after it is completely dissolved, add it dropwise to the above reaction system within 1 hour. After the addition is complete, raise the temperature to 65°C and continue the reflux reaction for 20 hours;

[008...

Embodiment 2

[0099] A kind of flame retardant containing DOPS / phosphazene structure, the preparation method of the described flame retardant containing DOPS / phosphazene structure comprises the following steps:

[0100] (a) Preparation of HAP

[0101] 1. HCCP and 4-hydroxybenzaldehyde are weighed according to the molar ratio of 1:6;

[0102] 2,3, with embodiment 1;

[0103] Finally, the product HAP was obtained as a white powdery solid with a melting point of 156.3-157.4° C., a yield of 97.2%, and a purity of >99.0%.

[0104] (b) Preparation of HAP-DOPS

[0105] 1. Weigh DOPS and HAP according to the molar ratio of 8:1;

[0106] 2. Use the mixed solution of organic solvent chlorobenzene and ethanol as the reaction medium, so that the reactants can fully react;

[0107] 3. Add the weighed DOPS into a four-necked flask equipped with a thermometer, condenser tube, stirrer and protective gas inlet and outlet, add an appropriate amount of solvent and triethylamine, install a reflux condensat...

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