阅读说明：本技术 一种反应型淀粉膨胀阻燃剂改性丙烯酸树脂和制备方法 (Reactive starch intumescent flame retardant modified acrylic resin and preparation method thereof ) 是由 李宇凡 于 2021-01-08 设计创作，主要内容包括：本发明涉及阻燃丙烯酸树脂技术领域,且公开了一种反应型淀粉膨胀阻燃剂改性丙烯酸树脂,磷酸铵化淀粉作为反应型膨胀阻燃剂加入到聚丙烯酸酯分子链中,提高了阻燃剂与丙烯酸树脂之间的界面作用力和亲和性,反应型阻燃剂有利于增强丙烯酸树脂的阻燃持久性,同时减少加入的阻燃剂对丙烯酸树脂材料的使用性能造成影响,磷酸铵化淀粉反应型膨胀阻燃剂,以淀粉作为膨胀碳源,磷酸酯基团作为酸源,三聚氰胺作为气源,在高温燃烧过程中,形成致密而连续的多孔泡沫焦炭层,抑制了氧气的渗透,起到了良好的隔绝氧气的作用,使丙烯酸树脂材料表现出优异的阻燃性。(The invention relates to the technical field of flame-retardant acrylic resin and discloses a reactive starch intumescent flame retardant modified acrylic resin, wherein ammonium phosphate starch is used as a reactive intumescent flame retardant and added into a polyacrylate molecular chain, the interfacial force and affinity between the flame retardant and the acrylic resin are improved, the reactive flame retardant is beneficial to enhancing the flame retardant durability of the acrylic resin, simultaneously reduces the influence of the added flame retardant on the service performance of the acrylic resin material, the ammonium phosphate starch reaction type intumescent flame retardant takes starch as an intumescent carbon source, phosphate group as an acid source and melamine as an air source, in the high-temperature combustion process, a compact and continuous porous foam coke layer is formed, so that the permeation of oxygen is inhibited, a good oxygen isolation effect is achieved, and the acrylic resin material shows excellent flame retardance.)

1. A reactive starch intumescent flame retardant modified acrylic resin is characterized in that: the preparation method of the reactive starch intumescent flame retardant modified acrylic resin comprises the following steps:

(1) adding soluble starch and phosphorus oxychloride into a 1, 4-dioxane solvent, carrying out a phosphorylation reaction, filtering the solvent, and washing with diethyl ether to obtain chlorinated phosphate-based starch;

(2) adding chlorinated phosphate-based starch and melamine into a 1, 4-dioxane solvent, carrying out amination substitution reaction, filtering the solvent, and washing with diethyl ether to obtain ammonium phosphate starch;

(3) adding ammonium phosphate starch into a distilled water solvent, adding butyl acrylate, methyl methacrylate and acrylic acid after ultrasonic dispersion is uniform, adding aqueous hydrogen peroxide and ferrous sulfate, carrying out a photoinitiation reaction, and centrifugally washing the mixture with distilled water until the upper layer is clear to obtain the reactive starch intumescent flame retardant grafted polyacrylate;

(4) and adding the reactive starch intumescent flame retardant grafted polyacrylate, the defoaming agent dimethyl silicone oil, the thickening agent dicyclohexyl phthalate and the antioxidant 330 into an acetone solvent, and performing a high-speed emulsification process to obtain the reactive starch intumescent flame retardant modified acrylic resin.

2. The reactive starch intumescent flame retardant modified acrylic resin as claimed in claim 1, wherein: the mass ratio of the soluble starch to the phosphorus oxychloride in the step (1) is 100: 120-180.

3. The reactive starch intumescent flame retardant modified acrylic resin as claimed in claim 1, wherein: the temperature of the phosphorylation reaction in the step (1) is 40-60 ℃, and the reaction time is 4-8 h.

4. The reactive starch intumescent flame retardant modified acrylic resin as claimed in claim 1, wherein: the mass ratio of the chlorinated phosphate-based starch to the melamine in the step (2) is 100: 20-40.

5. The reactive starch intumescent flame retardant modified acrylic resin as claimed in claim 1, wherein: the temperature of the amination substitution reaction in the step (2) is 40-60 ℃, and the reaction time is 2-6 h.

6. The reactive starch intumescent flame retardant modified acrylic resin as claimed in claim 1, wherein: the mass ratio of the ammonium phosphate starch, the butyl acrylate, the methyl methacrylate, the acrylic acid, the hydrogen peroxide and the ferrous sulfate in the step (3) is 30-60:60-100:100:10-25:4-12: 5-15.

7. The reactive starch intumescent flame retardant modified acrylic resin as claimed in claim 1, wherein: the light source of the photoinitiated reaction in the step (3) is ultraviolet light, the reaction temperature is 30-50 ℃, and the reaction time is 1-3 h.

8. The reactive starch intumescent flame retardant modified acrylic resin as claimed in claim 1, wherein: the mass ratio of the reactive starch intumescent flame retardant grafted polyacrylate, the defoaming agent dimethyl silicone oil, the thickening agent dicyclohexyl phthalate and the antioxidant 330 in the step (4) is 100:0.5-2:0.2-1: 0.2-0.6.

Technical Field

The invention relates to the technical field of flame-retardant acrylic resin, in particular to reactive starch intumescent flame retardant modified acrylic resin and a preparation method thereof.

Background

The acrylic resin is a thermoplastic or thermosetting resin, the thermoplastic acrylic resin is not crosslinked in the film forming process, has good gloss and color retention, good water resistance and chemical resistance and convenient construction, is widely applied to the fields of electric appliances, machinery, buildings and the like, the thermosetting acrylic resin has good fullness, glossiness and hardness, high weather resistance and solvent resistance, and is widely applied to products such as automobiles, bicycles, rolled steel and the like, but the traditional acrylic resin has poor flame retardance and easy combustion, and simultaneously generates a large amount of toxic gas in the combustion process, so the development and application of the acrylic resin are limited, and the flame retardance of the acrylic resin material needs to be further improved.

The flame retardant can effectively improve the flame retardance of polymer materials such as acrylic resin and the like, the traditional flame retardance mainly comprises a brominated flame retardant, a nitrogen-phosphorus flame retardant, a silicon flame retardant and the like, wherein the intumescent flame retardant mainly comprises an acid source, a carbon source and a gas source, a porous foam coke layer is formed on the surface of the material to achieve an excellent natural effect, and the intumescent flame retardant can be divided into an additive flame retardant and a reactive flame retardant according to an adding mode, wherein the reactive flame retardant is used as a polymerization monomer and participates in a polymerization reaction process to enable the polymer material to contain flame retardant components, so that the flame retardant has the advantages of lasting flame retardant property and small influence on the service performance of the polymer material.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a reactive starch intumescent flame retardant modified acrylic resin and a preparation method thereof, and solves the problem of poor flame retardance of the acrylic resin.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a reactive starch intumescent flame retardant modified acrylic resin is prepared by the following steps:

(1) adding soluble starch and phosphorus oxychloride into a 1, 4-dioxane solvent, carrying out phosphorylation reaction, filtering the solvent, and washing with diethyl ether to obtain the chlorinated phosphate-based starch.

(2) Adding chlorinated phosphate starch and melamine into a 1, 4-dioxane solvent, carrying out amination substitution reaction, filtering the solvent, and washing with diethyl ether to obtain the ammonium phosphate starch.

(3) Adding ammonium phosphate starch into a distilled water solvent, adding butyl acrylate, methyl methacrylate and acrylic acid after ultrasonic dispersion is uniform, adding aqueous hydrogen peroxide and ferrous sulfate, carrying out a photoinitiation reaction, and centrifugally washing with distilled water until the upper layer is clear to obtain the reactive starch intumescent flame retardant grafted polyacrylate.

(4) And adding the reactive starch intumescent flame retardant grafted polyacrylate, the defoaming agent dimethyl silicone oil, the thickening agent dicyclohexyl phthalate and the antioxidant 330 into an acetone solvent, and performing a high-speed emulsification process to obtain the reactive starch intumescent flame retardant modified acrylic resin.

Preferably, the mass ratio of the soluble starch to the phosphorus oxychloride in the step (1) is 100: 120-180.

Preferably, the temperature of the phosphorylation reaction in the step (1) is 40-60 ℃, and the reaction time is 4-8 h.

Preferably, the mass ratio of the chlorinated phosphate-based starch to the melamine in the step (2) is 100: 20-40.

Preferably, the temperature of the amination substitution reaction in the step (2) is 40-60 ℃, and the reaction time is 2-6 h.

Preferably, the mass ratio of the ammonium phosphate starch, the butyl acrylate, the methyl methacrylate, the acrylic acid, the hydrogen peroxide and the ferrous sulfate in the step (3) is 30-60:60-100:100:10-25:4-12: 5-15.

Preferably, the light source of the photoinitiated reaction in the step (3) is ultraviolet light, the reaction temperature is 30-50 ℃, and the reaction time is 1-3 h.

Preferably, the mass ratio of the reactive starch intumescent flame retardant grafted polyacrylate, the defoaming agent dimethyl silicone oil, the thickening agent dicyclohexyl phthalate and the antioxidant 330 in the step (4) is 100:0.5-2:0.2-1: 0.2-0.6.

(III) advantageous technical effects

Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:

in the reactive starch intumescent flame retardant modified acrylic resin, phosphorus oxychloride and starch are subjected to a crosslinking reaction to obtain chlorinated phosphate starch, chlorine atoms and amino groups of melamine are subjected to a substitution reaction to generate ammonium phosphate groups to obtain ammonium phosphate starch, and then, in a Fenton reagent initiation system consisting of hydrogen peroxide and ferrous sulfate, introducing ammonium phosphate starch to generate active free radicals through ultraviolet irradiation to attack an acrylic acid monomer, then carrying out free radical polymerization, and carrying out in-situ polymerization on the ammonium phosphate starch and polyacrylate, so that the ammonium phosphate starch is added into a polyacrylate molecular chain as a reactive intumescent flame retardant, the interfacial force and the affinity between the flame retardant and the acrylic resin are improved, the reactive flame retardant is favorable for enhancing the flame retardant durability of the acrylic resin, and the influence of the added flame retardant on the service performance of the acrylic resin material is reduced.

This reaction type starch intumescent flame retardant modified acrylic resin, ammonium phosphate starch reaction type intumescent flame retardant, regard starch as the inflation carbon source, phosphate group is as the acid source, melamine is as the air supply, in the high temperature combustion process, form compact and continuous porous foam coke layer, the infiltration of oxygen has been inhibited, good isolated oxygen's effect has been played, melamine high temperature pyrolysis produces a large amount of non-combustible nature gases such as ammonia and nitrogen gas simultaneously, the concentration of oxygen around the material has been diluted, the process of further inhibition burning, under the synergistic action, make the acrylic resin material show excellent fire resistance.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: a reactive starch intumescent flame retardant modified acrylic resin is prepared by the following steps:

(1) adding soluble starch and phosphorus oxychloride into a 1, 4-dioxane solvent in a mass ratio of 100:120-180, carrying out phosphorylation reaction for 4-8h at 40-60 ℃, filtering the solvent, and washing with diethyl ether to obtain the chlorinated phosphate-based starch.

(2) Adding chlorinated phosphate-based starch and melamine in a mass ratio of 100:20-40 into a 1, 4-dioxane solvent, carrying out amination substitution reaction for 2-6h at 40-60 ℃, filtering the solvent, and washing with diethyl ether to obtain the ammonium phosphate starch.

(3) Adding ammonium phosphate starch into a distilled water solvent, adding butyl acrylate, methyl methacrylate and acrylic acid after uniform ultrasonic dispersion, adding aqueous hydrogen peroxide and ferrous sulfate, controlling the mass ratio of the ammonium phosphate starch, the butyl acrylate, the methyl methacrylate, the acrylic acid, the hydrogen peroxide and the ferrous sulfate to be 30-60:60-100:100:10-25:4-12:5-15, carrying out light-induced reaction for 1-3 hours at 30-50 ℃ by taking ultraviolet as a light source, and centrifugally washing by distilled water until the upper layer is clear to obtain the reactive starch intumescent flame retardant grafted polyacrylate.

(4) Adding reactive starch intumescent flame retardant grafted polyacrylate, defoaming agent dimethyl silicone oil, thickening agent dicyclohexyl phthalate and antioxidant 330 into an acetone solvent in a mass ratio of 100:0.5-2:0.2-1:0.2-0.6, and performing a high-speed emulsification process to obtain the reactive starch intumescent flame retardant modified acrylic resin.

Example 1

(1) Adding soluble starch and phosphorus oxychloride into a 1, 4-dioxane solvent in a mass ratio of 100:120, performing phosphorylation reaction for 4 hours at 40 ℃, filtering the solvent, and washing with diethyl ether to obtain the chlorinated phosphate-based starch.

(2) Adding chlorinated phosphate-based starch and melamine in a mass ratio of 100:20 into a 1, 4-dioxane solvent, carrying out amination substitution reaction for 2 hours at 40 ℃, filtering the solvent, and washing with diethyl ether to obtain the ammonium phosphate starch.

(3) Adding ammonium phosphate starch into a distilled water solvent, adding butyl acrylate, methyl methacrylate and acrylic acid after uniform ultrasonic dispersion, adding aqueous hydrogen peroxide and ferrous sulfate, controlling the mass ratio of the ammonium phosphate starch, the butyl acrylate, the methyl methacrylate, the acrylic acid, the hydrogen peroxide and the ferrous sulfate to be 30:60:100:10:4:5, carrying out a photoinitiation reaction for 1h at 30 ℃ by taking ultraviolet as a light source, and centrifugally washing the distilled water until the upper layer is clear to obtain the reactive starch intumescent flame retardant grafted polyacrylate.

(4) Adding reactive starch intumescent flame retardant grafted polyacrylate, defoaming agent dimethyl silicone oil, thickening agent dicyclohexyl phthalate and antioxidant 330 into an acetone solvent in a mass ratio of 100:0.5:0.2:0.2, and performing a high-speed emulsification process to obtain the reactive starch intumescent flame retardant modified acrylic resin.

Example 2

(1) Adding soluble starch and phosphorus oxychloride into a 1, 4-dioxane solvent in a mass ratio of 100:140, performing phosphorylation reaction for 6 hours at 50 ℃, filtering the solvent, and washing with diethyl ether to obtain the chlorinated phosphate-based starch.

(2) Adding chlorinated phosphate-based starch and melamine in a mass ratio of 100:25 into a 1, 4-dioxane solvent, carrying out amination substitution reaction for 6 hours at 60 ℃, filtering the solvent, and washing with diethyl ether to obtain the ammonium phosphate starch.

(3) Adding ammonium phosphate starch into a distilled water solvent, adding butyl acrylate, methyl methacrylate and acrylic acid after uniform ultrasonic dispersion, adding aqueous hydrogen peroxide and ferrous sulfate, controlling the mass ratio of the ammonium phosphate starch, the butyl acrylate, the methyl methacrylate, the acrylic acid, the hydrogen peroxide and the ferrous sulfate to be 40:75:100:15:7:8, carrying out 2-hour photoinitiation reaction at 50 ℃ by taking ultraviolet as a light source, and centrifugally washing the distilled water until the upper layer is clear to obtain the reactive starch intumescent flame retardant grafted polyacrylate.

(4) Adding reactive starch intumescent flame retardant grafted polyacrylate, defoaming agent dimethyl silicone oil, thickening agent dicyclohexyl phthalate and antioxidant 330 into an acetone solvent in a mass ratio of 100:1:0.5:0.3, and performing a high-speed emulsification process to obtain the reactive starch intumescent flame retardant modified acrylic resin.

Example 3

(1) Adding soluble starch and phosphorus oxychloride into a 1, 4-dioxane solvent in a mass ratio of 100:160, performing phosphorylation reaction for 6 hours at 50 ℃, filtering the solvent, and washing with diethyl ether to obtain the chlorinated phosphate-based starch.

(2) Adding chlorinated phosphate-based starch and melamine in a mass ratio of 100:32 into a 1, 4-dioxane solvent, carrying out amination substitution reaction for 4 hours at 50 ℃, filtering the solvent, and washing with diethyl ether to obtain the ammonium phosphate starch.

(3) Adding ammonium phosphate starch into a distilled water solvent, adding butyl acrylate, methyl methacrylate and acrylic acid after uniform ultrasonic dispersion, adding aqueous hydrogen peroxide and ferrous sulfate, controlling the mass ratio of the ammonium phosphate starch, the butyl acrylate, the methyl methacrylate, the acrylic acid, the hydrogen peroxide and the ferrous sulfate to be 50:90:100:20:10:12, carrying out 2-hour photoinitiation reaction at 40 ℃ by taking ultraviolet as a light source, and centrifugally washing distilled water until the upper layer is clear to obtain the reactive starch intumescent flame retardant grafted polyacrylate.

(4) Adding reactive starch intumescent flame retardant grafted polyacrylate, defoaming agent dimethyl silicone oil, thickening agent dicyclohexyl phthalate and antioxidant 330 into an acetone solvent in a mass ratio of 100:1.5:0.8:0.5, and performing a high-speed emulsification process to obtain the reactive starch intumescent flame retardant modified acrylic resin.

Example 4

(1) Adding soluble starch and phosphorus oxychloride into a 1, 4-dioxane solvent in a mass ratio of 100:180, performing phosphorylation reaction for 8 hours at 60 ℃, filtering the solvent, and washing with diethyl ether to obtain the chlorinated phosphate-based starch.

(2) Adding chlorinated phosphate-based starch and melamine in a mass ratio of 100:40 into a 1, 4-dioxane solvent, carrying out amination substitution reaction for 6 hours at 60 ℃, filtering the solvent, and washing with diethyl ether to obtain the ammonium phosphate starch.

(3) Adding ammonium phosphate starch into a distilled water solvent, adding butyl acrylate, methyl methacrylate and acrylic acid after uniform ultrasonic dispersion, adding aqueous hydrogen peroxide and ferrous sulfate, controlling the mass ratio of the ammonium phosphate starch, the butyl acrylate, the methyl methacrylate, the acrylic acid, the hydrogen peroxide and the ferrous sulfate to be 60:100:100:25:12:15, carrying out a photoinitiation reaction for 3 hours at 50 ℃ by taking ultraviolet as a light source, and centrifugally washing the distilled water until the upper layer is clear to obtain the reactive starch intumescent flame retardant grafted polyacrylate.

(4) Adding reactive starch intumescent flame retardant grafted polyacrylate, defoaming agent dimethyl silicone oil, thickening agent dicyclohexyl phthalate and antioxidant 330 into an acetone solvent in a mass ratio of 100:2:1:0.6, and performing a high-speed emulsification process to obtain the reactive starch intumescent flame retardant modified acrylic resin.

Comparative example 1

(1) Adding soluble starch and phosphorus oxychloride into a 1, 4-dioxane solvent in a mass ratio of 1:1, carrying out phosphorylation reaction for 6 hours at 50 ℃, filtering the solvent, and washing with diethyl ether to obtain the chlorinated phosphate-based starch.

(2) Adding chlorinated phosphate-based starch and melamine in a mass ratio of 100:15 into a 1, 4-dioxane solvent, carrying out amination substitution reaction for 6 hours at 50 ℃, filtering the solvent, and washing with diethyl ether to obtain the ammonium phosphate starch.

(3) Adding ammonium phosphate starch into a distilled water solvent, adding butyl acrylate, methyl methacrylate and acrylic acid after uniform ultrasonic dispersion, adding aqueous hydrogen peroxide and ferrous sulfate, controlling the mass ratio of the ammonium phosphate starch, the butyl acrylate, the methyl methacrylate, the acrylic acid, the hydrogen peroxide and the ferrous sulfate to be 20:50:100:5:2:3, carrying out 2-hour photoinitiation reaction at 40 ℃ by taking ultraviolet as a light source, and centrifugally washing distilled water until the upper layer is clear to obtain the reactive starch intumescent flame retardant grafted polyacrylate.

(4) Adding reactive starch intumescent flame retardant grafted polyacrylate, defoaming agent dimethyl silicone oil, thickening agent dicyclohexyl phthalate and antioxidant 330 into an acetone solvent in a mass ratio of 100:0.2:0.1:0.1, and performing a high-speed emulsification process to obtain the reactive starch intumescent flame retardant modified acrylic resin.

Comparative example 2

(1) Adding soluble starch and phosphorus oxychloride in a mass ratio of 1:2 into a 1, 4-dioxane solvent, carrying out phosphorylation reaction for 6 hours at 50 ℃, filtering the solvent, and washing with diethyl ether to obtain the chlorinated phosphate-based starch.

(2) Adding chlorinated phosphate-based starch and melamine in a mass ratio of 100:45 into a 1, 4-dioxane solvent, carrying out amination substitution reaction for 6 hours at 60 ℃, filtering the solvent, and washing with diethyl ether to obtain the ammonium phosphate starch.

(3) Adding ammonium phosphate starch into a distilled water solvent, adding butyl acrylate, methyl methacrylate and acrylic acid after uniform ultrasonic dispersion, adding aqueous hydrogen peroxide and ferrous sulfate, controlling the mass ratio of the ammonium phosphate starch, the butyl acrylate, the methyl methacrylate, the acrylic acid, the hydrogen peroxide and the ferrous sulfate to be 70:120:100:30:15:18, carrying out a photoinitiation reaction for 3 hours at 50 ℃ by taking ultraviolet as a light source, and centrifugally washing the distilled water until the upper layer is clear to obtain the reactive starch intumescent flame retardant grafted polyacrylate.

(4) Adding reactive starch intumescent flame retardant grafted polyacrylate, defoaming agent dimethyl silicone oil, thickening agent dicyclohexyl phthalate and antioxidant 330 into an acetone solvent in a mass ratio of 100:2.5:1.3:0.75, and performing a high-speed emulsification process to obtain the reactive starch intumescent flame retardant modified acrylic resin.

A KJ-3095 horizontal and vertical combustion testing machine is used for testing the flame retardant performance of the reactive starch intumescent flame retardant modified acrylic resin, and the test standard is fire-retardant rating UL 94.