阅读说明：本技术 一种聚氨酯发泡产品用阻燃异氰酸根混合物 (Flame-retardant isocyanate mixture for polyurethane foaming product ) 是由 陈峻 崔青天 于 2020-08-07 设计创作，主要内容包括：本发明公开了一种聚氨酯发泡产品用阻燃异氰酸根混合物,包含异氰酸酯、聚醚、聚乙二醇、含磷阻燃剂、亚铁盐溶液、铜盐溶液、浓硫酸和一氧化碳吸收剂,通过在混合物中添加Fe2+和Cu2+,实现游离异氰酸根的完全消耗,避免游离异氰酸根在燃烧时产生有毒气体,且形成的产物中包含亚铁氰化铜,当聚氨酯发泡产品表面受热燃烧时,亚铁氰化铜能够与浓硫酸反应生成CO,并通过一氧化碳吸收剂将CO转变为CO2,进一步提高材料的阻燃效果,且亚铁氰化铜在剧烈燃烧时产生的N2可以当做保护材料的惰性气体置换出空气中的氧气,防止材料燃烧或爆炸,阻燃效果更好,实用性更佳。(The invention discloses a flame-retardant isocyanic acid radical mixture for a polyurethane foaming product, which comprises isocyanate, polyether, polyethylene glycol, a phosphorus-containing flame retardant, a ferrous salt solution, a copper salt solution, concentrated sulfuric acid and a carbon monoxide absorbent, by adding Fe2+ and Cu2+ into the mixture, the complete consumption of free isocyanate is realized, the generation of toxic gas during the combustion of the free isocyanate is avoided, and the formed product contains copper ferrocyanide, when the surface of the polyurethane foaming product is heated and burned, the copper ferrocyanide can react with concentrated sulfuric acid to generate CO, and CO is converted into CO2 by the carbon monoxide absorbent, the flame retardant effect of the material is further improved, and N2 generated during the violent combustion of the copper ferrocyanide can be used as inert gas of a protective material to replace oxygen in the air, so that the material is prevented from being combusted or exploded, the flame retardant effect is better, and the practicability is better.)

1. A flame-retardant isocyanate mixture for polyurethane foaming products is characterized in that: the flame-retardant isocyanate mixture for the polyurethane foaming product comprises the following components in parts by weight: 20-30 parts of isocyanate, 20-30 parts of polyether, 0-15 parts of polyethylene glycol, 10-15 parts of phosphorus-containing flame retardant, 20-30 parts of ferrous salt solution, 5-10 parts of copper salt solution, 2-8 parts of concentrated sulfuric acid and 2-8 parts of carbon monoxide absorbent.

2. The flame-retardant isocyanate mixture for the polyurethane foam product as claimed in claim 1, wherein: the isocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, the content of the isocyanate in the isocyanate is 30-40%, and the content of free isocyanate in a product obtained by reacting the isocyanate with polyether is not more than 3%.

3. The flame-retardant isocyanate mixture for the polyurethane foam product as claimed in claim 1, wherein: the phosphorus-containing flame retardant is a mixture of melamine polyphosphate, graphite, flame-retardant polyether and white polyether, and the addition ratio of the melamine polyphosphate to the graphite to the mixture of the flame-retardant polyether and the white polyether is 1:1:10: 6.

4. The flame-retardant isocyanate mixture for the polyurethane foam product as claimed in claim 1, wherein: the content of Fe2+ in the ferrite solution is not less than 3%.

5. The flame-retardant isocyanate mixture for the polyurethane foam product as claimed in claim 1, wherein: the content of Cu2+ in the copper salt solution is not lower than the content of Fe2+ in the ferrous salt solution.

6. The flame-retardant isocyanate mixture for the polyurethane foam product as claimed in claim 1, wherein: the carbon monoxide absorbent is 54% copper diammine acetate.

7. A method for preparing a flame-retardant isocyanate mixture for polyurethane foam products as claimed in claim 1, wherein the flame-retardant isocyanate mixture comprises the following steps: the method comprises the following steps:

s1, putting 20-30 parts of isocyanate, 20-30 parts of polyether and 0-15 parts of polyethylene glycol into a reaction vessel provided with a reflux condenser tube and a stirrer, introducing nitrogen for protection, heating to 65 ℃, and reacting for 3 hours;

s2, reducing the pressure inside the reaction container, adding 5-7.5 parts of phosphorus-containing flame retardant into the reaction container when the pressure inside the reaction container is reduced to 0MPa, fully stirring, and cooling to room temperature to obtain a flame-retardant isocyanic acid radical product A;

s3, adding the isocyanic acid radical product A into a reaction container containing 20-30 parts of ferrous salt solution, adding a small amount of catalyst, heating to 80 ℃ for reaction for 1h, adding 5-10 parts of copper salt solution into the reaction container, and reacting until reddish brown precipitate is generated in the container;

s4, cooling the reaction container, adding 2-8 parts of concentrated sulfuric acid and 2-8 parts of carbon monoxide absorbent, fully stirring, heating to 30 ℃ for reaction until no bubbles are generated, and obtaining a flame-retardant isocyanic acid radical product B;

s5, carrying out deammoniation treatment and dehydration treatment on the isocyanate product B with flame retardance to obtain an isocyanate product C with flame retardance;

s6, adding the remaining 5-7.5 parts of phosphorus-containing flame retardant into the flame-retardant isocyanate product C, and fully stirring at room temperature to obtain the flame-retardant isocyanate mixture for the polyurethane foaming product.

8. The method for preparing the flame-retardant isocyanate mixture for the polyurethane foaming product as claimed in claim 7, wherein the flame-retardant isocyanate mixture comprises the following steps: the water content of the flame-retardant isocyanate product C is not more than 1%.

Technical Field

The invention relates to the technical field of macromolecules, in particular to a flame-retardant isocyanate mixture for a polyurethane foaming product.

Background

Present polyurethane foaming is fire retardant for product is mostly single phosphorus class fire retardant, phosphorus high temperature liquefaction forms the isolated air of oil film during the burning, but the phenomenon of pulling of phosphorus class fire retardant is comparatively serious, fire-retardant effect attenuates gradually along with the live time, if adopt isocyanate and fire-retardant polyether reaction, produce fire-retardant polyurea composition, then can fine solution phosphorus class fire retardant pull the problem, but isocyanate produces a large amount of free isocyanic radicals easily in the reaction sequence, isocyanic radical can produce toxic gas when burning, cause the injury to the human body, the security is not good.

Disclosure of Invention

The invention aims to provide a flame-retardant isocyanate mixture for a polyurethane foaming product, which has better flame-retardant effect and is safer in use, so as to solve the problems that isocyanate proposed in the background technology is easy to generate a large amount of free isocyanate in the reaction process, and the isocyanate generates toxic gas during combustion, so that the isocyanate is harmful to human bodies and has poor safety.

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

the flame-retardant isocyanate mixture for the polyurethane foaming product comprises the following components in parts by weight: 20-30 parts of isocyanate, 20-30 parts of polyether, 0-15 parts of polyethylene glycol, 10-15 parts of phosphorus-containing flame retardant, 20-30 parts of ferrous salt solution, 5-10 parts of copper salt solution, 2-8 parts of concentrated sulfuric acid and 2-8 parts of carbon monoxide absorbent.

Preferably, the isocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, the isocyanate content in the isocyanate is 30-40%, and the free isocyanate content in the product obtained by reacting the isocyanate with the polyether is not more than 3%.

Preferably, the phosphorus-containing flame retardant is a mixture of melamine polyphosphate, graphite, flame-retardant polyether and white polyether, and the addition ratio of the melamine polyphosphate to the mixture of the graphite to the mixture of the flame-retardant polyether to the white polyether is 1:1:10: 6.

Preferably, the content of Fe2+ in the ferrous salt solution is not less than 3%.

Preferably, the content of Cu2+ in the copper salt solution is not lower than the content of Fe2+ in the ferrous salt solution.

Preferably, the carbon monoxide absorbent is 54% copper diammine acetate.

The invention also provides a preparation method of the flame-retardant isocyanate mixture for the polyurethane foaming product, which comprises the following steps:

s1, putting 20-30 parts of isocyanate, 20-30 parts of polyether and 0-15 parts of polyethylene glycol into a reaction vessel provided with a reflux condenser tube and a stirrer, introducing nitrogen for protection, heating to 65 ℃, and reacting for 3 hours;

s2, reducing the pressure inside the reaction container, adding 5-7.5 parts of phosphorus-containing flame retardant into the reaction container when the pressure inside the reaction container is reduced to 0MPa, fully stirring, and cooling to room temperature to obtain a flame-retardant isocyanic acid radical product A;

s3, adding the isocyanic acid radical product A into a reaction container containing 20-30 parts of ferrous salt solution, adding a small amount of catalyst, heating to 80 ℃ for reaction for 1h, adding 5-10 parts of copper salt solution into the reaction container, and reacting until reddish brown precipitate is generated in the container;

s4, cooling the reaction container, adding 2-8 parts of concentrated sulfuric acid and 2-8 parts of carbon monoxide absorbent, fully stirring, heating to 30 ℃ for reaction until no bubbles are generated, and obtaining a flame-retardant isocyanic acid radical product B;

s5, carrying out deammoniation treatment and dehydration treatment on the isocyanate product B with flame retardance to obtain an isocyanate product C with flame retardance;

s6, adding the remaining 5-7.5 parts of phosphorus-containing flame retardant into the flame-retardant isocyanate product C, and fully stirring at room temperature to obtain the flame-retardant isocyanate mixture for the polyurethane foaming product.

Preferably, the water content of the flame retardant isocyanate product C is not more than 1%.

According to the flame-retardant isocyanate mixture for the polyurethane foaming product, provided by the invention, the complete consumption of free isocyanate is realized by adding Fe2+ and Cu2+ into the mixture, the generation of toxic gas during the combustion of the free isocyanate is avoided, the formed product contains copper ferrocyanide, when the surface of the polyurethane foaming product is heated and combusted, the copper ferrocyanide can react with concentrated sulfuric acid to generate CO, the CO is converted into CO2 through a carbon monoxide absorbent, the flame retardant effect of the material is further improved, N2 generated during the violent combustion of the copper ferrocyanide can be used as inert gas of a protective material to replace oxygen in the air, the material is prevented from being combusted or exploded, the flame retardant effect is better, and the practicability is better.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.