阅读说明：本技术 一种浴胶液以及微胶囊阻燃剂及其制备方法 (Bath glue solution, microcapsule flame retardant and preparation method thereof ) 是由 王少卿 张斌 曾少华 董炜 于 2019-12-03 设计创作，主要内容包括：本发明涉及环保消防以及新材料领域,尤其涉一浴胶液以及微胶囊阻燃剂及其制备方法,其特征在于,所述的微胶囊结构为囊壁是环氧树脂、囊芯是聚硅硼氧烷/聚磷酸铵杂化物。聚硅硼氧烷或聚磷酸铵杂化物在制备协同阻燃和防止二次燃烧的材质中的用途。本发明制备的阻燃剂为阻燃输送带产业的发展提供技术支持,具有高效阻燃、抑烟、耐水耐潮和优异的粘合性；同时添加量低、成本低,制备工艺简单,可工业化生产。(The invention relates to the field of environmental protection fire control and new materials, in particular to a glue bath solution, a microcapsule fire retardant and a preparation method thereof. Use of a polyborosiloxane or ammonium polyphosphate hybrid in the preparation of a material that is synergistically flame retardant and prevents afterburning. The flame retardant prepared by the invention provides technical support for the development of the flame-retardant conveyor belt industry, and has the advantages of high-efficiency flame retardance, smoke suppression, water resistance, moisture resistance and excellent adhesiveness; meanwhile, the additive amount is low, the cost is low, the preparation process is simple, and industrial production can be realized.)

1. A preparation method of a microcapsule flame retardant is characterized by comprising the following steps:

1) adding ammonium polyphosphate, tetraethoxysilane, boric acid and absolute ethyl alcohol into a reaction kettle, raising the temperature to 50-95 ℃, mechanically stirring for 10 min-10 h, adding water and dilute hydrochloric acid, adjusting the pH to 0.5-6.5, reacting for 1-6 h, cooling, filtering, washing and drying to obtain a polyborosiloxane/ammonium polyphosphate hybrid; 2) adding absolute ethyl alcohol, epoxy resin and aliphatic polyamine into a reaction kettle, mechanically stirring for 10 min-10 h, then adding a dispersing agent and the polyborosiloxane/ammonium polyphosphate hybrid in the step 1), mechanically stirring for 10 min-10 h, raising the temperature to 30-90 ℃, reacting for 1 h-6 h, cooling, filtering, washing and drying to obtain the epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule flame retardant.

2. The preparation method of the microcapsule flame retardant according to claim 1, wherein the dip solution is a bath solution, the bath solution comprises water, epoxy resin, isocyanate, epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsules, and the bath solution comprises the following raw materials in parts by weight: 10 to 80 parts of water, 0.1 to 10 parts of epoxy resin, 0.5 to 14 parts of isocyanate and 2 to 30 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule.

3. The method of claim 1, wherein the water is deionized water or distilled water; the adding amount of the ammonium polyphosphate in the step 1) is 2-60% of the weight of the tetraethoxysilane; the adding mass ratio of the ethyl orthosilicate to the boric acid in the step 1) is 1: 1-9: 1; the adding mass ratio of the ethyl orthosilicate to the absolute ethyl alcohol in the step 1) is 1: 1-1: 9; the mass ratio of the water to the absolute ethyl alcohol in the step 1) is 1: 1-1: 9; the concentration of the dilute hydrochloric acid in the step 1) is 5-40%.

4. The method for preparing a microencapsulated flame retardant as defined in claim 1, wherein the aliphatic polyamine in step 2) is one or more selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine; the addition amount of the epoxy resin is 5 to 30 percent of the mass of the epoxy resin; the dispersing agent in the step 2) is sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene, and the mass ratio of the sodium dodecyl benzene sulfonate to the alkylphenol polyoxyethylene is 1: 1-9: 1; the addition amount of the polyborosiloxane/ammonium polyphosphate hybrid is 5 to 30 percent of the mass of the polyborosiloxane/ammonium polyphosphate hybrid.

5. The method for preparing a microencapsulated flame retardant as defined in claim 1, wherein the ratio of the polyborosiloxane/ammonium polyphosphate hybrid to the epoxy resin in step 2) is 1: 1-1: 9; the mass ratio of the epoxy resin to the absolute ethyl alcohol in the step 2) is 1: 1-1: 9.

6. the medium isocyanate in the dipping solution according to claim 2 is blocked aqueous isocyanate.

7. The microcapsule flame retardant is characterized in that the microcapsule structure is that the capsule wall is made of epoxy resin, and the capsule core is made of polyborosiloxane/ammonium polyphosphate hybrid.

8. The bath gel solution is characterized by comprising water, epoxy resin, isocyanate, epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsules, wherein the bath gel solution comprises the following raw materials in parts by mass: 10 to 80 parts of water, 0.1 to 10 parts of epoxy resin, 0.5 to 14 parts of isocyanate and 2 to 30 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule.

9. Use of a polyborosiloxane and/or ammonium polyphosphate hybrid in the preparation of a material that synergistically retards flame and prevents afterburning.

10. The formula of the bath gel liquid is characterized in that the preparation method comprises one of the following steps:

technical scheme 1 a formula of a bath glue solution comprises the following raw materials in parts by weight: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 2 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule; the formula of the second bath glue solution comprises the following raw materials in parts by weight: 3 parts of water, 22.18 parts of latex, 1.2 parts of ammonia water and 24.12 parts of RF resin solution;

technical scheme 2 a formula of a bath glue solution comprises the following raw materials in parts by weight: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 6 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule; the formula of the second bath glue solution comprises the following raw materials in parts by weight: 3 parts of water, 22.18 parts of latex, 1.2 parts of ammonia water and 24.12 parts of RF resin solution;

technical scheme 3A formula of a bath glue solution comprises the following raw materials in parts by weight: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 12 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule; the formula of the second bath glue solution comprises the following raw materials in parts by weight: 3 parts of water, 22.18 parts of latex, 1.2 parts of ammonia water and 24.12 parts of RF resin solution;

technical scheme 4 a formula of a bath glue solution comprises the following raw materials in parts by weight: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 20 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule; the formula of the second bath glue solution comprises the following raw materials in parts by weight: 3 parts of water, 22.18 parts of latex, 1.2 parts of ammonia water and 24.12 parts of RF resin solution.

Technical Field

The invention relates to the field of environmental protection fire control and new materials, in particular to a bath gel liquid, a microcapsule fire retardant and a preparation method thereof.

Background

Ammonium polyphosphate has the defects of large hygroscopicity, poor affinity with a base material, easiness in migration, incapability of maintaining a flame retardant effect for a long time, poor thermal stability and the like due to the structural characteristics, and when a flame retardant with a single component is used for flame retarding the base material, the ammonium polyphosphate is difficult to maintain good mechanical properties under the condition of passing through the V-0(1.6mm) flame retardant grade of UL-94. Compared with the ammonium phosphate as the raw material, the microencapsulated flame retardant not only has greatly reduced water solubility, but also has better processing performance of the polymer material which is flame-retardant by the microencapsulated flame retardant, such as easy compatibility with the polymer, and even if the addition amount of the flame retardant is increased, the loss of the mechanical property of the material is less. These materials can be used as compatibilizers for polyolefins and their copolymers, saturated or unsaturated polyesters, polyamides, epoxy resins, etc.

The conveying belt has high operation efficiency and is a main means for underground transportation of coal mines, but the conveying belt is usually a main cause of fire. Coal producing countries in the world attach great attention and vigilance and adopt the technical measures of flame retardance. However, the fire retardant treatment of the conveyor belt is the key point of the conveyor belt industry, and the fire retardant treatment of the dipped canvas is the key point of the development of the fire retardant conveyor belt.

The problem of developing flame-retardant gummed canvas can be divided into two parts: the flame-retardant canvas is researched, and functional groups with flame-retardant functions are grafted in a fiber molecular chain to obtain flame-retardant fibers. The method can start from the fiber spinning stage, and the flame-retardant fiber can be synthesized by modern spinning technology. But the strength loss of the synthetic flame-retardant fiber is too high, the strength loss of the flame-retardant nylon wheel industrial yarn and the flame-retardant polyester industrial yarn is up to 30 percent basically, and the strength grade of the conveyer belt made of the flame-retardant fiber is too low to reach the use standard of the conveyer belt. Too high production costs are also an important reason why flame retardant fibers are difficult to apply on a large scale. And secondly, the flame retardant RFL dipping solution is used as a typical water-based latex dipping solution, so that the flame retardant property of dipped canvas is not improved.

Disclosure of Invention

The purpose of the invention is as follows: in order to provide a bath solution with better effect, a microcapsule flame retardant and a preparation method thereof, the specific purpose is seen in a plurality of substantial technical effects of the specific implementation part.

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

a preparation method of a microcapsule flame retardant is characterized by comprising the following steps: 1) adding ammonium polyphosphate, tetraethoxysilane, boric acid and absolute ethyl alcohol into a reaction kettle, raising the temperature to 50-95 ℃, mechanically stirring for 10 min-10 h, adding water and dilute hydrochloric acid into the reaction kettle, reacting for 1-6 h with the pH value of 0.5-6.5 in the system, cooling, filtering, washing and drying to obtain the polyborosiloxane/ammonium polyphosphate hybrid. 2) Firstly, adding absolute ethyl alcohol, epoxy resin and aliphatic polyamine into a reaction kettle, mechanically stirring for 10 min-10 h, then adding a polyborosiloxane/ammonium polyphosphate hybrid and a dispersing agent, mechanically stirring for 10 min-10 h, raising the temperature to 30-90 ℃, reacting for 1 h-6 h, cooling, filtering, washing and drying to obtain the epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule. The formula of the dipping solution is a bath solution, the bath solution comprises water, epoxy resin, isocyanate, epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsules, and the formula of the bath solution comprises the following raw materials in parts by weight: 10 to 80 parts of water, 0.1 to 10 parts of epoxy resin, 0.5 to 14 parts of isocyanate and 2 to 30 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule.

The invention further adopts the technical scheme that the water is deionized water and distilled water; the adding amount of the ammonium polyphosphate in the step 1) is 2-60% of the weight of the tetraethoxysilane; the adding mass ratio of the ethyl orthosilicate to the boric acid in the step 1) is 1: 1-9: 1; the adding mass ratio of the ethyl orthosilicate to the absolute ethyl alcohol in the step 1) is 1: 1-1: 9; the mass ratio of the water to the absolute ethyl alcohol in the step 1) is 1: 1-1: 9; the concentration of the dilute hydrochloric acid in the step 1) is 5-40%.

The further technical scheme of the invention is that the aliphatic polyamine in the step 2) is one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine; the addition amount of the epoxy resin is 5-30% of the mass of the epoxy resin.

The further technical scheme of the invention is that the dispersing agent in the step 2) is sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene, and the mass ratio of the sodium dodecyl benzene sulfonate to the alkylphenol polyoxyethylene is 1: 1-9: 1; the addition amount of the polyborosiloxane/ammonium polyphosphate hybrid is 5 to 30 percent of the mass of the polyborosiloxane/ammonium polyphosphate hybrid.

The further technical proposal of the invention is that the mass ratio of the polyborosiloxane/ammonium polyphosphate hybrid in the step 2) to the epoxy resin is 1: 1-1: 9.

the further technical scheme of the invention is that the mass ratio of the epoxy resin to the absolute ethyl alcohol in the step 2) is 1: 1-1: 9; the intermediate isocyanate of the dipping solution is blocked water-based isocyanate.

The invention further adopts the technical scheme that the formula of the gum dipping solution is a gum dipping solution, the gum dipping solution comprises water, epoxy resin, isocyanate, epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsules, and the formula of the gum dipping solution comprises the following raw materials in parts by mass: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 12 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule.

The microcapsule flame retardant is characterized in that the microcapsule structure is that the capsule wall is made of epoxy resin, and the capsule core is made of polyborosiloxane/ammonium polyphosphate hybrid.

Use of a polyborosiloxane and/or ammonium polyphosphate hybrid in the preparation of a material that synergistically retards flame and prevents afterburning.

An environment-friendly magnesium hydroxide microcapsule flame-retardant smoke suppressant is characterized in that the preparation method comprises one of the following steps:

technical scheme 1 a formula of a bath gel liquid comprises the following raw materials in parts by weight: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 2 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule; the formula of the second bath glue solution comprises the following raw materials in parts by weight: 3 parts of water, 22.18 parts of latex, 1.2 parts of ammonia water and 24.12 parts of resorcinol formaldehyde resin solution (RF resin solution); among them, the RF resin solution is commercially available.

Technical scheme 2 a formula of a bath gel liquid comprises the following raw materials in parts by weight: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 6 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule; the formula of the second bath glue solution comprises the following raw materials in parts by weight: 3 parts of water, 22.18 parts of latex, 1.2 parts of ammonia water and 24.12 parts of RF resin solution;

technical scheme 3 a formula of a bath gel liquid comprises the following raw materials in parts by weight: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 12 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule; the formula of the second bath glue solution comprises the following raw materials in parts by weight: 3 parts of water, 22.18 parts of latex, 1.2 parts of ammonia water and 24.12 parts of RF resin solution; a

Technical scheme 4 a formula of a bath gel liquid comprises the following raw materials in parts by weight: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 20 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule; the formula of the second bath glue solution comprises the following raw materials in parts by weight: 3 parts of water, 22.18 parts of latex, 1.2 parts of ammonia water and 24.12 parts of RF resin solution.

Compared with the prior art, the invention adopting the technical scheme has the following beneficial effects: the invention relates to a microcapsule flame retardant, (1) the solubility of ammonium polyphosphate in water can be effectively reduced; (2) improving the compatibility between the modified starch and the base material; (3) the mechanical property of the material can be improved by adding the microcapsule; (4) good flame retardant and smoke suppression performance.

The preparation method of the microcapsule flame retardant and the formula of the dipping solution adopt the epoxy resin microcapsule flame retardant to further improve the flame retardant property of the RFL dipping solution and the dispersion effect thereof, and provide technical support for the development of the flame-retardant conveyor belt industry.

The preparation method of the microcapsule flame retardant and the formula of the impregnation solution have the advantages of simple preparation process, high-efficiency flame retardance, low addition amount and low cost, are expected to realize industrial production, and have good popularization and application prospects.

A microcapsule flame retardant and its formula are disclosed, which features flame-retarding, smoke-suppressing, water-proof and moisture-proof, and excellent adhesion. The invention has higher use value, and the popularization and the application of the invention can bring greater economic and social benefits.

Drawings

To further illustrate the present invention, further description is provided below with reference to the accompanying drawings:

FIG. 1 formation of epoxy/polyborosiloxane/ammonium polyphosphate microencapsulated flame retardant;

FIG. 2 shows the morphology (a scanning electron microscope; b transmission electron microscope) of the epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule flame retardant;

FIG. 3 is Table 1.

Detailed Description

The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention. In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", "top", "bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, as they may be fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

The patent provides a plurality of parallel schemes, and different expressions belong to an improved scheme based on a basic scheme or a parallel scheme. Each solution has its own unique features.

The invention aims to provide a preparation method of a microcapsule flame retardant and application of the microcapsule flame retardant in a dipping solution, and the microcapsule flame retardant has the advantages of high flame retardant efficiency, excellent smoke suppression, low filling amount, excellent dispersibility, no damage to the mechanical property of a material, no toxicity, environmental protection, easily obtained raw materials, easy industrialization and capability of solving the difficulty of the conventional flame retardant technology.

In order to solve the technical problems, the invention adopts a technical scheme that: provides a preparation method of a microcapsule flame retardant and a formula of a gum dipping solution, and the preparation method comprises the following steps: 1) adding ammonium polyphosphate, tetraethoxysilane, boric acid and absolute ethyl alcohol into a reaction kettle, raising the temperature to 50-95 ℃, mechanically stirring for 10 min-10 h, adding water and dilute hydrochloric acid into the reaction kettle, reacting for 1-6 h with the pH value of 0.5-6.5 in the system, cooling, filtering, washing and drying to obtain the polyborosiloxane/ammonium polyphosphate hybrid. 2) Firstly, adding absolute ethyl alcohol, epoxy resin and aliphatic polyamine into a reaction kettle, mechanically stirring for 10 min-10 h, then adding a polyborosiloxane/ammonium polyphosphate hybrid and a dispersing agent, mechanically stirring for 10 min-10 h, raising the temperature to 30-90 ℃, reacting for 1 h-6 h, cooling, filtering, washing and drying to obtain the epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule. The formula of the dipping solution is a bath solution, the bath solution comprises water, epoxy resin, isocyanate, epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsules, and the formula of the bath solution comprises the following raw materials in parts by weight: 10 to 80 parts of water, 0.1 to 10 parts of epoxy resin, 0.5 to 14 parts of isocyanate and 2 to 30 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule.

In a preferred embodiment of the invention, the preparation of the microcapsule flame retardant and the formula of the impregnation solution are characterized in that the water is deionized water and distilled water.

In a preferred embodiment of the invention, the preparation of the microcapsule flame retardant and the formula of the dipping solution are characterized in that the addition amount of the ammonium polyphosphate in the step 1) is 2-60% of the mass of the tetraethoxysilane.

In a preferred embodiment of the invention, the preparation of the microcapsule flame retardant and the formula of the dipping solution are characterized in that the adding amount of the tetraethoxysilane/boric acid in the step 1) is that the mass ratio of the tetraethoxysilane/boric acid is 1: 1-9: 1.

in a preferred embodiment of the invention, the preparation of the microcapsule flame retardant and the formula of the dipping solution are characterized in that the adding amount of the tetraethoxysilane/absolute ethyl alcohol in the step 1) is that the mass ratio of the tetraethoxysilane/absolute ethyl alcohol is 1: 1-1: 9.

in a preferred embodiment of the invention, the preparation and the formula of the impregnation solution of the microcapsule flame retardant are characterized in that the addition amount of the water/absolute ethyl alcohol in the step 1) is that the mass ratio of the water/absolute ethyl alcohol is 1: 1-1: 9.

in a preferred embodiment of the present invention, the preparation of the microcapsule flame retardant and the formula of the dipping solution are characterized in that the concentration of the dilute hydrochloric acid in the step 1) is 5% to 40%.

In a preferred embodiment of the present invention, the preparation of the microencapsulated flame retardant and the formulation of the dip solution are characterized in that the aliphatic polyamine in step 2) is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, etc. The addition amount of the epoxy resin is 5-30% of the mass of the epoxy resin.

In a preferred embodiment of the invention, the preparation of the microcapsule flame retardant and the formula of the dipping solution are characterized in that the dispersant in the step 2) is sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene, and the mass ratio of the sodium dodecyl benzene sulfonate to the alkylphenol polyoxyethylene is 1: 1 to 9: 1. the addition amount of the polyborosiloxane/ammonium polyphosphate hybrid is 5 to 30 percent of the weight of the polyborosiloxane/ammonium polyphosphate hybrid

In a preferred embodiment of the invention, the preparation and the dip formula of the microcapsule flame retardant are characterized in that the mass ratio of the polyborosiloxane/ammonium polyphosphate hybrid in the step 2) to the epoxy resin is 1: 1-1: 9.

in a preferred embodiment of the invention, the preparation of the microcapsule flame retardant and the formula of the dipping solution are characterized in that the mass ratio of the epoxy resin to the absolute ethyl alcohol in the step 2) is 1: 1-1: 9.

in a preferred embodiment of the invention, the preparation of the microcapsule flame retardant and the formula of the dipping solution are characterized in that isocyanate in the dipping solution is blocked water-based isocyanate.

In a preferred embodiment of the invention, the preparation and dip formula of the microcapsule flame retardant are characterized in that the microcapsule structure is that the capsule wall is made of epoxy resin, and the capsule core is made of a polyborosiloxane/ammonium polyphosphate hybrid.

In a preferred embodiment of the present invention, the preparation of the microcapsule flame retardant and the formula of the dipping solution are characterized in that the formula of the dipping solution is a bath solution, the bath solution comprises water, epoxy resin, isocyanate, epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsules, and the formula of the bath solution comprises the following raw materials by weight: 46.75 parts of water, 0.55 part of epoxy resin, 2.7 parts of isocyanate and 12 parts of epoxy resin/polyborosiloxane/ammonium polyphosphate microcapsule.