阅读说明：本技术 一种磷-硅-氮三元协同阻燃剂及制备方法 (Phosphorus-silicon-nitrogen ternary synergistic flame retardant and preparation method thereof ) 是由 颜红侠 郭留龙 白天 王莲莲 张渊博 于 2019-09-11 设计创作，主要内容包括：本发明涉及一种磷-硅-氮三元协同阻燃剂及制备方法,相比传统的多元素协同阻燃剂制备方法步骤繁琐,可能使用大量溶剂和催化剂,难以大规模工业化生产；而多数热固性树脂阻燃效果较差,若要提高其阻燃性,需要添加大量阻燃剂提高其阻燃性能的问题,本发明利用含氨基的烷氧基硅烷、磷酸三烷氧基酯和二乙醇胺(及其衍生物),采用“一锅法”在无溶剂、无催化剂的条件下制备新型磷-硅-氮协同高效阻燃剂,且符合绿色化学的发展要求。本发明的有益效果是：反应过程不使用溶剂和催化剂,反应时间短、操作容易、成本低、所用设备简单、实用性强。(The invention relates to a phosphorus-silicon-nitrogen ternary synergistic flame retardant and a preparation method thereof, compared with the traditional preparation method of the multielement synergistic flame retardant, the preparation method has the disadvantages of complicated steps, possible use of a large amount of solvents and catalysts, and difficult large-scale industrial production; the invention relates to a novel phosphorus-silicon-nitrogen synergistic efficient flame retardant, which is prepared by using amino-containing alkoxy silane, trialkoxy phosphate and diethanol amine (and derivatives thereof) and adopting a one-pot method under the conditions of no solvent and no catalyst and meets the development requirement of green chemistry. The invention has the beneficial effects that: the reaction process does not use solvent and catalyst, and has short reaction time, easy operation, low cost, simple equipment and strong practicability.)

1. A phosphorus-silicon-nitrogen ternary synergistic flame retardant is characterized by comprising 1-3: 3-6 molar ratio of amino-containing tri-functionality alkoxy silane, phosphoric acid trialkoxy ester, diethanol amine and derivatives thereof; the structural formula is as follows:

2. the phosphorus-silicon-nitrogen ternary synergistic flame retardant of claim 1, wherein: the amino-containing alkoxysilane contains an amino group, including but not limited to: (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane or 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane.

3. the phosphorus-silicon-nitrogen ternary synergistic flame retardant of claim 1, wherein: the trialkoxy phosphate contains three alkoxy groups including, but not limited to: trimethyl phosphate, triethyl phosphate, tripropyl phosphate or tributyl phosphate.

4. The phosphorus-silicon-nitrogen ternary synergistic flame retardant of claim 1, wherein: the glycol amine contains nitrogen and two hydroxyl groups, including but not limited to: diethanolamine or N-methyldiethanolamine.

5. A method for preparing the phosphorus-silicon-nitrogen ternary synergistic flame retardant of claim 1, which is characterized by comprising the following steps:

step 1: reacting trifunctional alkoxy silane containing amino, trialkoxy phosphate, diethanol amine and derivatives thereof at a molar ratio of 1-3: 3-6 at 80-200 ℃ for 4-12 hours under the protection of nitrogen until no distillate is produced;

Step 2: and adding the obtained product into a dialysis bag with the molecular weight of 1000-2000, dialyzing for 24-48 hours, and performing rotary evaporation to obtain the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

Technical Field

the invention belongs to the technical field of advanced polymer material science, and relates to a phosphorus-silicon-nitrogen ternary synergistic flame retardant and a preparation method thereof.

Background

with the development of industry and the demand for environmental protection, conventional halogen-containing flame retardants have been abandoned due to environmental hazards and biotoxicity to mammals, and phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, inorganic flame retardants, and the like have been substituted for these flame retardants. Phosphorus flame retardants are concerned because of their high flame retardant efficiency and small addition; the nitrogen flame retardant can be degraded when being heated, absorbs heat and generates gas to play a role in diluting combustible gas; the organic silicon flame retardant has the advantages of good thermal stability, environmental friendliness and good flame retardant effect. Along with the development requirement of the multifunctionalization of the flame retardant, the performance of the flame retardant containing a single flame-retardant element is improved to a limited extent, the flame retardant requirement under a severe condition is difficult to meet, and a more excellent flame retardant effect can be achieved through the synergistic effect of different flame-retardant elements. Research shows that the phosphorus-nitrogen flame retardant can form an air source, a carbon source and an acid source to form three elements of the intumescent flame retardant, and the intumescent flame retardant has good flame retardant potential; when the phosphorus-silicon flame retardants are used together, high-viscosity polyphosphoric acid is generated when phosphorus-containing compounds or groups are thermally decomposed, the silicon-containing flame retardants have lower surface energy and can migrate to the surface of a base material in a high-temperature molten state, and due to the bridging effect, the polyphosphoric acid can be cooperated to form an inorganic carbon layer which has higher viscosity and contains Si-O, Si-C, so that the exchange of substances and the heat exchange are blocked, and the excellent flame retardant performance is shown. The patent CN105175780A relates to a preparation method of an acrylate flame retardant containing nitrogen, phosphorus and silicon and a flame-retardant epoxy acrylate coating thereof, the inventor uses a semi-adduct of toluene-2, 4-diisocyanate and hydroxyethyl acrylate, GMA phosphate and trimethylchlorosilane to react to obtain the flame retardant, and the flame retardant is used for preparing the epoxy acrylate coating, so that the flame retardant has good flame retardance and excellent mechanical property and impact resistance. However, the preparation process of the flame retardant in the patent is complicated, and is not beneficial to industrial large-scale production. The patent CN107698765A relates to a cyclotriphosphazene flame retardant containing nitrogen, phosphorus and silicon and a preparation method thereof, the inventor dissolves hexachlorocyclotriphosphazene in tetrahydrofuran solution, adds phenol into the tetrahydrofuran solution, adds hydroxyl silicone oil into the tetrahydrofuran solution after reacting for a period of time, and reacts to obtain the nitrogen-phosphorus-containing cyclotriphosphazene flame retardant. The fire retardant combines the advantages of organic and inorganic fire retardants and has a multi-element synergistic fire retardant effect. However, the hexachlorocyclotriphosphazene serving as a reaction raw material is a volatile toxic compound, a large amount of phenol is used in the reaction process, and chlorine-containing components still remain in reaction products, so that certain toxic gas is generated in the use process of the flame retardant, the use effect is influenced, and the development requirement of green chemistry is difficult to meet.

Disclosure of Invention

Technical problem to be solved

In order to avoid the defects of the prior art, the invention provides a phosphorus-silicon-nitrogen ternary synergistic flame retardant and a preparation method thereof, and the multielement synergistic flame retardant is widely adopted by people according to the limited flame retardant effect of the single element flame retardant. Aiming at the problems that the preparation process of the nitrogen-phosphorus-silicon synergistic flame retardant is complicated at the present stage and volatile toxic solvent and catalyst are needed in the reaction process, the simple and easy green preparation method is simple and easy, and the flame retardant effect can be obviously improved by multi-element synergy.

Technical scheme

A phosphorus-silicon-nitrogen ternary synergistic flame retardant is characterized by comprising 1-3: 3-6 molar ratio of amino-containing tri-functionality alkoxy silane, phosphoric acid trialkoxy ester, diethanol amine and derivatives thereof; the structural formula is as follows:

The amino-containing alkoxysilane contains an amino group, including but not limited to: (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane or 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane.

The trialkoxy phosphate contains three alkoxy groups including, but not limited to: trimethyl phosphate, triethyl phosphate, tripropyl phosphate or tributyl phosphate.

The glycol amine contains nitrogen and two hydroxyl groups, including but not limited to: diethanolamine or N-methyldiethanolamine.

A method for preparing the phosphorus-silicon-nitrogen ternary synergistic flame retardant is characterized by comprising the following steps:

step 1: reacting trifunctional alkoxy silane containing amino, trialkoxy phosphate, diethanol amine and derivatives thereof at a molar ratio of 1-3: 3-6 at 80-200 ℃ for 4-12 hours under the protection of nitrogen until no distillate is produced;

step 2: and adding the obtained product into a dialysis bag with the molecular weight of 1000-2000, dialyzing for 24-48 hours, and performing rotary evaporation to obtain the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

Advantageous effects

Compared with the traditional preparation method of the multi-element synergistic flame retardant, the phosphorus-silicon-nitrogen ternary synergistic flame retardant and the preparation method thereof have the advantages that the steps are complex, a large amount of solvents and catalysts are possibly used, and large-scale industrial production is difficult; the invention relates to a novel phosphorus-silicon-nitrogen synergistic efficient flame retardant, which is prepared by using amino-containing alkoxy silane, trialkoxy phosphate and diethanol amine (and derivatives thereof) and adopting a one-pot method under the conditions of no solvent and no catalyst and meets the development requirement of green chemistry. The invention has the beneficial effects that: the reaction process does not use solvent and catalyst, and has short reaction time, easy operation, low cost, simple equipment and strong practicability.

the phosphorus-silicon-nitrogen ternary synergistic flame retardant with different functional groups such as hydroxyl, phosphate group, aminopropyl and the like at the end position can be prepared by adjusting the raw material ratio. The flame retardant belongs to an organic flame retardant, has good compatibility with high polymer materials, can be used in the fields of paper, cloth, fiber, plastic, resin and the like, and has wide application prospect.

Detailed Description

the invention will now be further described with reference to the examples:

the traditional preparation method of the multi-element synergistic flame retardant has complicated steps, may use a large amount of solvents and catalysts, and is difficult to realize large-scale industrial production; most thermosetting resins have poor flame retardant effect, and a large amount of flame retardant needs to be added to improve the flame retardant property if the flame retardant property is to be improved. Therefore, the invention utilizes the amino-containing alkoxy silane, the phosphoric acid trialkoxy ester and the diethanol amine (and derivatives thereof) to prepare the novel phosphorus-silicon-nitrogen synergistic high-efficiency flame retardant by a one-pot method under the conditions of no solvent and no catalyst, and meets the development requirement of green chemistry.

The specific method comprises the following steps:

The first step is as follows: adding amino-containing trifunctional alkoxy silane, trialkoxy phosphate and diethanolamine (and derivatives thereof) into a three-neck flask according to a molar ratio of 1-3: 3-6, stirring under the protection of nitrogen, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours until no distillate is produced.

And secondly, adding the product obtained in the first step into a dialysis bag with the molecular weight of 1000-2000, dialyzing for 24-48 hours, and then performing rotary evaporation to obtain the final product, namely the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

Example 1 was carried out:

adding (3-aminopropyl) trimethoxysilane, trimethyl phosphate and diethanol amine into a three-neck flask according to the molar ratio of 1:1:3, stirring under the protection of nitrogen, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours until no distillate is produced. And adding the obtained product into a dialysis bag with the molecular weight of 2000, dialyzing for 24 hours, and performing rotary evaporation to obtain the final product, namely the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

example 2 was carried out:

Adding (3-aminopropyl) trimethoxysilane, triethyl phosphate and N-methyldiethanolamine into a three-neck flask according to the molar ratio of 1:1:3, stirring under the protection of nitrogen, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours until no distillate is produced. And adding the obtained product into a dialysis bag with the molecular weight of 2000, dialyzing for 24 hours, and performing rotary evaporation to obtain the final product, namely the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

Example 3 of implementation:

Adding (3-aminopropyl) triethoxysilane, triethyl phosphate and diethanolamine into a three-neck flask according to a molar ratio of 1:1:3, stirring under the protection of nitrogen, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours until no distillate is produced. And adding the obtained product into a dialysis bag with the molecular weight of 2000, dialyzing for 24 hours, and performing rotary evaporation to obtain the final product, namely the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

Example 4 of implementation:

Adding (3-aminopropyl) triethoxysilane, triethyl phosphate and N-methyldiethanolamine into a three-neck flask according to a molar ratio of 1:1:5, stirring under the protection of nitrogen, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours until no distillate is produced. And adding the obtained product into a dialysis bag with the molecular weight of 2000, dialyzing for 24 hours, and performing rotary evaporation to obtain the final product, namely the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

Example 5 was carried out:

Adding 3- (2-aminoethylamino) propyl trimethoxy silane, trimethyl phosphate and diethanol amine into a three-neck flask according to a molar ratio of 1:1:3, stirring under the protection of nitrogen, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours until no distillate is produced. And adding the obtained product into a dialysis bag with the molecular weight of 2000, dialyzing for 24 hours, and performing rotary evaporation to obtain the final product, namely the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

Example 6 of implementation:

Adding 3- (2-aminoethylamino) propyl trimethoxy silane, trimethyl phosphate and N-methyldiethanolamine into a three-neck flask according to the molar ratio of 1:1:3, stirring under the protection of nitrogen, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours until no distillate is generated. And adding the obtained product into a dialysis bag with the molecular weight of 2000, dialyzing for 24 hours, and performing rotary evaporation to obtain the final product, namely the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

Example 7 was carried out:

adding 3- (2-aminoethylamino) propyl trimethoxy silane, triethyl phosphate and diethanol amine into a three-neck flask according to a molar ratio of 1:1:3, stirring under the protection of nitrogen, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours until no distillate is produced. And adding the obtained product into a dialysis bag with the molecular weight of 2000, dialyzing for 24 hours, and performing rotary evaporation to obtain the final product, namely the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

example 8 was carried out:

Adding 3- (2-aminoethylamino) propyl trimethoxy silane, triethyl phosphate and N-methyldiethanolamine into a three-neck flask according to a molar ratio of 1:1:5, stirring under the protection of nitrogen, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours until no distillate is generated. And adding the obtained product into a dialysis bag with the molecular weight of 2000, dialyzing for 48 hours, and performing rotary evaporation to obtain the final product, namely the phosphorus-silicon-nitrogen ternary synergistic flame retardant.

by adjusting the molar ratio among the alkoxy silane, the phosphoric acid trialkoxy ester and the diethanol amine (and derivatives thereof) and the type of the alkoxy silane, the phosphorus-silicon-nitrogen synergistic flame retardant with hydroxyl, phosphate and aminopropyl at the terminal position can be respectively obtained.

The components designed by the invention and the technological parameter chain participating in the reaction are reasonable and can complete the reaction. Otherwise, the unreasonable selection of the component parameters can not achieve the purpose and effect of the invention. As in the following examples:

Example 9 was carried out:

Adding (3-aminopropyl) trimethoxysilane, trimethyl phosphate and diethanol amine into a three-neck flask according to the molar ratio of 1:1:3, stirring under the protection of nitrogen, controlling the reaction temperature to be below 80 ℃, and reacting for 4-12 hours without producing distillate.

example 10 of implementation:

adding (3-aminopropyl) trimethoxy silane, trimethyl phosphate and diethanol amine into a three-neck flask according to the molar ratio of 1:1:3, stirring under the protection of nitrogen, controlling the reaction temperature to be more than 200 ℃, and reacting for 4-12 hours to generate a gel phenomenon.

example 11 of implementation:

adding (3-aminopropyl) trimethoxysilane, trimethyl phosphate and diethanol amine into a three-neck flask according to the molar ratio of 1:1:3, stirring under the condition of no nitrogen protection, controlling the reaction temperature to be 80-200 ℃, and reacting for 4-12 hours to generate gel.