阅读说明：本技术 一种聚烯烃用新型阻燃剂及其制备方法 (Novel flame retardant for polyolefin and preparation method thereof ) 是由 陈荣 闻辉 于 2020-11-25 设计创作，主要内容包括：本发明公开一种聚烯烃用新型阻燃剂及制备方法,属于阻燃剂领域。该阻燃剂制备方法：一、将植酸和水加入到反应器中、搅拌,将二苯基甲基哌嗪和2,6-二氨基吡啶分别加热融化,然后同时滴加到反应器中反应,反应物析出过滤得到粗产品,干燥得到中间体；二、将中间体在惰性气体条件下进行脱水缩合反应后得到最终产物。本发明合成的新型阻燃剂具有良好的稳定性、耐水解性,可用于提高聚烯烃类树脂的阻燃性能。(The invention discloses a novel flame retardant for polyolefin and a preparation method thereof, belonging to the field of flame retardants. The preparation method of the flame retardant comprises the following steps: firstly, adding phytic acid and water into a reactor, stirring, respectively heating and melting diphenylmethylpiperazine and 2, 6-diaminopyridine, then simultaneously dripping into the reactor for reaction, separating out reactants, filtering to obtain a crude product, and drying to obtain an intermediate; and secondly, carrying out dehydration condensation reaction on the intermediate under the condition of inert gas to obtain a final product. The novel flame retardant synthesized by the invention has good stability and hydrolysis resistance, and can be used for improving the flame retardant property of polyolefin resin.)

1. A novel flame retardant for polyolefins, characterized in that the structural formula of the flame retardant is:

wherein m is a positive integer of 1 to 100.

2. A preparation method of a novel flame retardant for polyolefin is characterized by comprising the following steps:

a. adding 2 parts of phytic acid into 5-30 parts of water in parts by mole, and stirring to fully dissolve the phytic acid;

b. heating and melting diphenylmethylpiperazine and 2, 6-diaminopyridine respectively;

c. respectively dripping the substances obtained in the step b into the mixture obtained in the step a at the same time, and stirring;

d. adjusting the solution system obtained in the step c to pH 6-8 with ammonia water, after finishing dripping, heating for continuous reaction until the reaction is finished, cooling, and filtering to obtain a white precipitate intermediate;

e. heating the intermediate obtained in the step d under the condition of inert gas to carry out dehydration condensation reaction to obtain a reaction product;

f. and cooling the obtained reaction product to room temperature, and crushing to obtain the novel flame retardant for polyolefin.

3. The method of claim 2, wherein the molar ratio of the diphenylmethylpiperazine, 2, 6-diaminopyridine to the phytic acid is 7.6-8.2: 0.8-11: 2.

4. The method as claimed in claim 2, wherein the melting temperature of diphenylmethylpiperazine in step b is 90-100 ℃ and the melting temperature of 2, 6-diaminopyridine is 120-130 ℃.

5. The method of claim 2, wherein the temperature increase in step d is a uniform temperature increase, and the temperature increase is 80-100 ℃.

6. The method for preparing a novel flame retardant for polyolefin according to claim 2, wherein the reaction time of step d is 1-2 h.

7. The method for preparing a novel flame retardant for polyolefins according to claim 2, wherein the heating temperature of the dehydration condensation reaction in step e is 250-270 ℃.

8. The method of claim 2, wherein the time of the dehydration condensation reaction in step e is 0.5-2 h.

9. The method of claim 2, wherein the particle size of the powder obtained by pulverizing in step f is not greater than 80 μm.

Technical Field

The invention belongs to the technical field of flame retardants, and particularly relates to a novel flame retardant for polyolefin and a preparation method thereof.

Background

The polyolefin is a high polymer material with the largest output and the most extensive application due to the abundant raw materials, low price, easy processing and forming and excellent comprehensive performance. Among them, polyethylene and polypropylene are most important. However, polyolefin is of a carbon chain skeleton structure, and after being ignited, the polyolefin reacts with oxygen in the air, the carbon chain skeleton collapses at a high speed, the chain segment structure decomposes to form a large amount of toxic smoke, and heat is released, so that the polyolefin threatens lives and properties of people greatly. In order to solve the above problems, flame resistance of polyolefin materials has been improved, flame retardant technology has been developed for more than half a century, and flame retardants have been continuously generated and applied to various products.

The flame retardant is an auxiliary agent for endowing the flammable polymer with flame retardancy, and can be divided into an additive flame retardant and a reactive flame retardant according to the production action mode. According to the specific composition, the flame retardant may be an inorganic flame retardant, a halogen flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, or the like. Compared with halogen flame retardants, the phosphorus and nitrogen flame retardants have less harm to the environment during production, and after the phosphorus and nitrogen flame retardants are added into polymers, the smoke and the released toxic and harmful gases generated during combustion are less, so the phosphorus and nitrogen flame retardants have better environmental protection effect.

The nitrogenous phosphate flame retardant belongs to phosphorus and nitrogen flame retardants, and can generate non-combustible gas such as polymetaphosphoric acid and N2 and the like by thermal decomposition, wherein the polymetaphosphoric acid has high-efficiency dehydration property and can promote polymer dehydration to form a carbon layer, the non-combustible gas can enable the carbon layer to expand and foam, and a finally formed compact expansion layer can effectively prevent heat and oxygen so as to generate a flame retardant effect, so that the nitrogenous phosphate flame retardant is a good acid source, is also an excellent char forming agent, has the function of a foaming agent and has high flame retardant efficiency.

However, the phosphorus and nitrogen flame retardants sold in the market have large addition amount in polyolefin, low thermal stability, easy yellowing and low carbon formation, and can achieve better flame retardant effect by adding multiple flame retardants in a compounding way. Therefore, the development of a flame retardant with high thermal stability and small addition amount has very important practical significance.

However, the phosphorus and nitrogen flame retardants sold in the market have large addition amount in polyolefin, low thermal stability, easy yellowing and low carbon formation, and can achieve better flame retardant effect by adding multiple flame retardants in a compounding way. Therefore, the development of a flame retardant with high thermal stability and small addition amount has very important practical significance.

Disclosure of Invention

The invention aims to provide a novel flame retardant for polyolefin and a preparation method thereof. The preparation method is simple, the yield is high, no organic solvent is used, and the production process is environment-friendly.

The novel flame retardant for polyolefin is characterized in that the structural formula of the flame retardant is as follows:

wherein m is a positive integer of 1 to 100.

The invention discloses a preparation method of a novel flame retardant for polyolefin, which is characterized by comprising the following steps:

a. adding 2 parts of phytic acid into 5-30 parts of water in parts by mole, and stirring to fully dissolve the phytic acid;

b. heating and melting diphenylmethylpiperazine and 2, 6-diaminopyridine respectively;

c. respectively dripping the substances obtained in the step b into the mixture obtained in the step a at the same time, and stirring;

d. adjusting the solution system obtained in the step c to pH 6-8 with ammonia water, after finishing dripping, heating for continuous reaction until the reaction is finished, cooling to room temperature, and filtering to obtain a white precipitate intermediate;

e. heating the intermediate obtained in the step d under the condition of inert gas to carry out dehydration condensation reaction to obtain a reaction product;

f. and cooling the obtained reaction product to room temperature, and crushing to obtain the novel flame retardant for polyolefin.

The mol ratio of the diphenyl methyl piperazine, the 2, 6-diaminopyridine to the phytic acid is 7.6-8.2: 0.8-1.1: 2.

in the step b, the heating and melting temperature of the diphenylmethylpiperazine is 90-100 ℃, and the heating and melting temperature of the 2, 6-diaminopyridine is 120-130 ℃.

And d, uniformly heating in the step d, wherein the heating temperature is 80-100 ℃.

The reaction time of the step d is 1-2 h.

The heating temperature of the dehydration condensation reaction in the step e is 250-270 ℃.

The time of the dehydration condensation reaction in the step e is 0.5-2 h.

And f, the particle size of the powder obtained after the grinding in the step f is not more than 80 um.

Detailed Description

Example 1

This embodiment provides a novel flame retardant for polyolefins, the structural formula of the flame retardant is:

wherein m is a positive integer of 1 to 100.

Example 2

The invention relates to a preparation method of a novel flame retardant for polyolefin, which comprises the following steps: a. adding 2 parts of phytic acid into 5 parts of water in parts by mole, and stirring to fully dissolve the phytic acid;

b. heating 7.6 parts of diphenylmethylpiperazine to melt at 90 ℃, and heating 0.8 part of 2, 6-diaminopyridine to melt at 120 ℃;

c. respectively dripping the substances obtained in the step b into the mixture obtained in the step a at the same time, and stirring;

d. adjusting the solution system obtained in the step c to pH 6 with ammonia water, after the dropwise addition is completed, heating to 80 ℃, continuously reacting for 2 hours, cooling to room temperature, and filtering to obtain a white precipitate intermediate;

e. heating the intermediate obtained in the step d to 250 ℃ under the condition of inert gas, and carrying out dehydration condensation reaction for 1h to obtain a reaction product;

f. and cooling the obtained reaction product to room temperature, and crushing the reaction product to obtain the novel flame retardant for polyolefin, wherein the crushed particle size of the reaction product is not more than 80 microns.

Example 3

The invention relates to a preparation method of a novel flame retardant for polyolefin, which comprises the following steps:

a. adding 2 parts of phytic acid into 10 parts of water in parts by mole, and stirring to fully dissolve the phytic acid;

b. heating 8 parts of diphenylmethylpiperazine at 95 ℃ to melt, and heating 1 part of 2, 6-diaminopyridine at 125 ℃ to melt;

c. respectively dripping the substances obtained in the step b into the mixture obtained in the step a at the same time, and stirring;

d. adjusting the solution system obtained in the step c to pH 8 with ammonia water, after the dropwise addition is completed, heating to 90 ℃, continuously reacting for 2 hours, cooling to room temperature, and filtering to obtain a white precipitate intermediate;

e. heating the intermediate obtained in the step d to 260 ℃ under the condition of inert gas, and carrying out dehydration condensation reaction for 1h to obtain a reaction product;

f. and cooling the obtained reaction product to room temperature, and crushing the reaction product to obtain the novel flame retardant for polyolefin, wherein the crushed particle size of the reaction product is not more than 80 microns.

Example 4

The invention relates to a preparation method of a novel flame retardant for polyolefin, which comprises the following steps:

a. adding 2 parts of phytic acid into 20 parts of water in parts by mole, and stirring to fully dissolve the phytic acid;

b. heating 7.6 parts of diphenylmethylpiperazine to melt at 100 ℃, and heating 1.1 parts of 2, 6-diaminopyridine to melt at 130 ℃;

c. respectively dripping the substances obtained in the step b into the mixture obtained in the step a at the same time, and stirring;

d. adjusting the solution system obtained in the step c to pH 7 with ammonia water, after the dropwise addition is completed, heating to 95 ℃, continuously reacting for 1.5h, cooling to room temperature, and filtering to obtain a white precipitate intermediate;

e. heating the intermediate obtained in the step d to 260 ℃ under the condition of inert gas, and carrying out dehydration condensation reaction for 0.5h to obtain a reaction product;

f. and cooling the obtained reaction product to room temperature, and crushing the reaction product to obtain the novel flame retardant for polyolefin, wherein the crushed particle size of the reaction product is not more than 80 microns.

Example 5

The invention relates to a preparation method of a novel flame retardant for polyolefin, which comprises the following steps:

a. adding 2 parts of phytic acid into 30 parts of water in parts by mole, and stirring to fully dissolve the phytic acid;

b. heating 8.2 parts of diphenylmethylpiperazine at 100 ℃ to melt, and heating 1.1 parts of 2, 6-diaminopyridine at 130 ℃ to melt;

c. respectively dripping the substances obtained in the step b into the mixture obtained in the step a at the same time, and stirring;

d. adjusting the solution system obtained in the step c to pH 8 with ammonia water, after the dropwise addition is finished, heating to 100 ℃, continuously reacting for 1h, cooling to room temperature, and filtering to obtain a white precipitate intermediate;

e. heating the intermediate obtained in the step d to 270 ℃ under the condition of inert gas, and carrying out dehydration condensation reaction for 0.5h to obtain a reaction product;

f. and cooling the obtained reaction product to room temperature, and crushing the reaction product to obtain the novel flame retardant for polyolefin, wherein the crushed particle size of the reaction product is not more than 80 microns.