阅读说明：本技术 一种三源一体型生物质改性膨胀阻燃剂及其制备方法、应用 (Three-source integrated biomass modified intumescent flame retardant and preparation method and application thereof ) 是由 王旭 陈思 吴飞洋 俞陈诚 马猛 施燕琴 何荟文 于 2020-04-13 设计创作，主要内容包括：本发明涉及阻燃剂的设计合成技术领域,尤其涉及一种三源一体型生物质改性膨胀阻燃剂及其制备方法、应用,所述三源一体型生物质改性膨胀阻燃剂,具有以下的结构通式：<Image he="532" wi="431" file="DDA0002448383140000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>式中,G为质子化后的核苷,其中n＝1000～2000。本发明以聚磷酸铵和生物质核苷为原料,聚磷酸铵作为酸源,核苷由碱基和五碳糖连接而成,是一种集气源和炭源于一体的天然生物质,两者通过简单的离子反应最终得到三源一体型膨胀阻燃剂。(The invention relates to the technical field of design and synthesis of flame retardants, in particular to a three-source integrated biomass modified intumescent flame retardant, and a preparation method and application thereof, wherein the three-source integrated biomass modified intumescent flame retardant has the following structural general formula: wherein G is a protonated nucleoside, and n is 1000-2000. The invention takes ammonium polyphosphate and biomass nucleoside as raw materials, the ammonium polyphosphate is taken as an acid source, and the nucleoside consists of basic groups andthe five-carbon sugar is formed by connecting five carbon sugars, is a natural biomass integrating a gas source and a carbon source, and finally obtains the three-source integrated intumescent flame retardant through simple ionic reaction.)

1. The three-source integrated biomass modified intumescent flame retardant is characterized by comprising the following structural general formula:

wherein G is a protonated nucleoside, and n is 1000-2000.

2. The biomass modified intumescent flame retardant of claim 1, wherein said nucleoside is one or more selected from adenosine, cytidine and guanosine.

3. The preparation method of the three-source integrated biomass modified intumescent flame retardant of claim 1 or 2, characterized by comprising the following steps:

(1) adding nucleoside into a hydrochloric acid solution with the pH value of 2-4, and stirring and dissolving to obtain a nucleoside solution;

(2) dispersing ammonium polyphosphate in ethanol to obtain ammonium polyphosphate turbid liquid;

(3) slowly adding ammonium polyphosphate turbid solution into the nucleoside solution for reaction;

(4) after the reaction is finished, cooling the reaction system to room temperature, filtering, washing with an organic solvent, filtering, and drying to obtain the three-source integrated biomass modified intumescent flame retardant.

4. The preparation method of the three-source integrated biomass modified intumescent flame retardant of claim 3, wherein the mass ratio of ammonium polyphosphate to nucleoside is 1 (0.2-0.6).

5. The preparation method of the three-source integrated biomass modified intumescent flame retardant of claim 3, wherein in the step (1), the mass ratio of the distilled water to the nucleoside is (5-10): 1.

6. the preparation method of the three-source integrated biomass modified intumescent flame retardant of claim 3, wherein in the step (2), the mass ratio of ammonium polyphosphate to ethanol is 1: (5-15).

7. The preparation method of the three-source integrated biomass modified intumescent flame retardant of claim 3, wherein in the step (3), the reaction temperature is 40-70 ℃ and the reaction time is 4-7 h.

8. The preparation method of the tri-source integrated biomass modified intumescent flame retardant of claim 3, wherein in the step (4), the organic solvent is methanol, ethanol or acetonitrile.

9. The preparation method of the three-source integrated biomass modified intumescent flame retardant of claim 3, wherein in the step (4), the mass ratio of the organic solvent to the ammonium polyphosphate is (5-10): 1.

10. The use of the tri-source-integrated biomass modified intumescent flame retardant of claim 1 or 2 in flame retardant articles, wherein the amount of the tri-source-integrated biomass modified intumescent flame retardant added in the flame retardant articles is not more than 20 wt%.

Technical Field

The invention relates to the technical field of design and synthesis of flame retardants, in particular to a three-source integrated biomass modified intumescent flame retardant, and a preparation method and application thereof.

Background

In the present society, polymer materials are widely used in aspects of life and production due to their excellent properties, but the serious drawback of flammability gradually emerges in the process of using polymer materials, and the drawback of flammability limits the application of polymer materials to a great extent, so that it is very important for flame retardant modification of polymers.

With the progress of human society, people have more and more strict requirements on the flame retardant modification of high polymers. In recent years, in the flame retardant modification of high polymers, compared with the defects that halogen flame retardants can release toxic and harmful gases and the addition demand of inorganic flame retardants is large, the intumescent flame retardant has the relatively most effective effect. The intumescent flame retardant generally comprises three parts, namely an acid source, a gas source and a carbon source, wherein the main flame retardant mechanism is that when the combustion temperature reaches a certain critical value, the acid source decomposes strong acid to act the carbon source into a carbon layer to cover the surface of a substrate to form a heat insulation protective layer, the gas source also releases some non-combustible gas to dilute combustible gas, and the three interact with each other, so that when the paired carbon layers are generated to be sufficiently compact, the combustion of the substrate is weakened or even extinguished, and the flame retardant effect is achieved.

In the existing intumescent flame retardant, ammonium polyphosphate (APP) occupies a very important position as an acid source, but although ammonium polyphosphate can decompose a strong acid substance at high temperature, the flame retardant effect of the ammonium polyphosphate used alone is not ideal, and the problems of low flame retardant efficiency, poor compatibility with a matrix material, large addition amount requirement, high cost and the like exist.

Chinese patent literature discloses a melamine nucleotide fire retardant and a preparation method thereof, and application publication number is CN107118388A, the melamine nucleotide fire retardant is synthesized by chemical reaction between nucleotide and melamine, the fire retardant has obvious fire retardant effect, but the vertical burning grade of the composite material can only be upgraded from no grade to V-2 grade, and high-efficiency fire retardation can not be achieved.

Chinese patent literature discloses a flame-retardant biodegradable resin/nucleotide composite material and a preparation method thereof, and the application publication number is CN 106433054A. However, this invention has a disadvantage of a large amount of flame retardant to be added.

Disclosure of Invention

The invention provides a three-source integrated biomass modified intumescent flame retardant which is low in addition amount, excellent in compatibility, green and environment-friendly in raw material source and integrates an acid source, a carbon source and a gas source into a whole, and aims to solve the problems of low flame retardant efficiency, poor compatibility with a base material, high addition amount and high cost of the traditional ammonium polyphosphate flame retardant.

The invention also provides a preparation method of the three-source integrated biomass modified intumescent flame retardant, which has no special requirements on equipment, is simple to operate and is easy to industrialize.

The invention also provides application of the three-source integrated biomass modified intumescent flame retardant in flame-retardant products.

In order to achieve the purpose, the invention adopts the following technical scheme:

the three-source integrated biomass modified intumescent flame retardant is characterized by comprising the following structural general formula:

wherein G is a protonated nucleoside, and n is 1000-2000.

The raw materials used by the three-source integrated biomass modified intumescent flame retardant are ammonium polyphosphate and biomass nucleoside, wherein the ammonium polyphosphate is a commonly used acid source in the intumescent flame retardant, the nucleoside is formed by connecting basic groups and pentose, the nucleoside is natural biomass integrating a gas source and a carbon source, and the three-source integrated intumescent flame retardant is finally obtained by simple ionic reaction of the ammonium polyphosphate and the nucleoside. The introduced biomass nucleoside has no negative influence on the ecological environment, and the application of the biomass nucleoside conforms to the great trend of green environmental protection and sustainable development.

Preferably, the nucleoside is selected from one or more of adenosine, cytidine and guanosine.

The structural formula of the nucleoside is shown as follows:

a preparation method of a three-source integrated biomass modified intumescent flame retardant comprises the following steps:

(1) adding nucleoside into a hydrochloric acid solution with the pH value of 2-4, and stirring and dissolving to obtain a nucleoside solution;

(2) dispersing ammonium polyphosphate in ethanol to obtain ammonium polyphosphate turbid liquid;

(3) slowly adding ammonium polyphosphate turbid solution into the nucleoside solution for reaction; the reaction mechanism is that modified nucleoside ammonium polyphosphate is obtained through the reaction between the phosphate group of ammonium polyphosphate and the protonated amino group of nucleoside;

(4) after the reaction is finished, cooling the reaction system to room temperature, filtering, washing with an organic solvent, filtering, and drying to obtain the three-source integrated biomass modified intumescent flame retardant.

At present, with the increasing consumption of energy, people face the crisis of energy shortage all the time, people are more and more strongly conscious of saving and environmental protection, and the concept of sustainable development is gradually deepened into the heart, so that the ammonium polyphosphate is modified on the basis of the saving, environmental protection, green and sustainable development, and the renewable biological resource nucleoside is utilized to modify the ammonium polyphosphate through simple reaction to prepare the three-source integrated biomass modified intumescent flame retardant to improve the flame retardant efficiency of the ammonium polyphosphate. The preparation method of the three-source integrated biomass modified intumescent flame retardant has the advantages of simple steps, mild conditions, no special requirements on equipment, high yield and easy large-scale industrial development.

Preferably, the mass ratio of the ammonium polyphosphate to the nucleoside is 1 (0.2-0.6). The mass ratio of the ammonium polyphosphate to the nucleoside is only limited in the above ratio range, the obtained flame retardant has good performance, too low addition of the nucleoside can cause too little carbon source and can not achieve the purpose of improving the flame retardant efficiency, and too high addition of the nucleoside can cause too little acid source and can also reduce the flame retardant effect.

Preferably, in the step (1), the mass ratio of the hydrochloric acid solution with the pH of 2-4 to the nucleoside is (5-10): 1.

preferably, in the step (2), the mass ratio of the ammonium polyphosphate to the ethanol is 1: (5-15).

Preferably, in the step (3), the reaction temperature is 40-70 ℃ and the reaction time is 4-7 h. .

Preferably, in step (4), the organic solvent is methanol, ethanol or acetonitrile. Ethanol is more preferred. The organic solvent is selected based on whether the unmodified ammonium polyphosphate can be washed.

Preferably, in the step (4), the mass ratio of the organic solvent to the ammonium polyphosphate is 5-10: 1.

When the addition amount of the three-source integrated biomass modified intumescent flame retardant in the flame-retardant product is not more than 20 wt% and the addition amount of the three-source integrated biomass modified intumescent flame retardant in the flame-retardant product is 20 wt%, the vertical combustion grade is FV-0 grade (3mm) and the oxygen index can reach more than 30, so that the effect is greatly improved compared with that of unmodified ammonium polyphosphate, the addition amount is reduced, the cost is saved, and the loss of the mechanical property of the material caused by the large addition amount of the flame retardant is avoided.

Therefore, the invention has the following beneficial effects:

(1) ammonium polyphosphate and biomass nucleoside are used as raw materials, the ammonium polyphosphate is used as an acid source, the nucleoside is formed by connecting basic groups and pentose, the natural biomass integrates a gas source and a carbon source, and the gas source and the carbon source are subjected to simple ionic reaction to finally obtain the three-source integrated intumescent flame retardant;

(2) the preparation method has simple steps, mild conditions, no special requirements on equipment, high yield and easy large-scale industrial development;

(3) when the addition amount of the three-source integrated biomass modified intumescent flame retardant in the flame-retardant product is 20 wt%, the vertical combustion grade is FV-0 grade (3mm) and the oxygen index can reach more than 30, so that the effect is greatly improved compared with that of unmodified ammonium polyphosphate, the addition amount is reduced, the cost is saved, and the loss of the mechanical property of the material caused by the large addition amount of the flame retardant is avoided.

Drawings

FIG. 1 is an infrared comparison graph of the triple-source integrated biomass modified intumescent flame retardant (a), ammonium polyphosphate (b) and guanosine (c) prepared in example 1.

Detailed Description

The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.

In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.

In the following examples and comparative examples of the invention, the flame retardant performance is tested according to GB/T2408-2008 and GB/T2406.2-2009, and the tensile strength is tested according to GB/T1040.1-2006.