阅读说明：本技术 一种聚氨酯发泡产品用阻燃聚醚材料 (Flame-retardant polyether material 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聚醚材料,使用磷酸甲酚脂基聚醚多元醇和三聚氰胺基聚醚多元醇的混合材料作为阻燃剂的材料基底,磷酸甲酚脂基聚醚多元醇中含有的苯环结构,能够有效提高聚氨酯发泡产品的力学性能,且分子硬段和分子软段的含量都跟大,提高聚氨酯发泡产品的闭孔率,三聚氰胺基聚醚多元醇中的三聚氰胺衍生物具有良好的热稳定性,提高聚氨酯发泡产品的耐火性,采用氢氧化铝将两种醇类基底材料进行混合,提高聚氨酯发泡产品材料表面的阻燃性能,氢氧化铝在材料表面形成膜状结构,能够在阻燃的同时对聚氨酯发泡产品材料内部进行保温,降低聚氨酯发泡产品材料的导热系数和吸水率,更加适用于产品保温。(The invention discloses a flame-retardant polyether material for polyurethane foam products, which uses a mixed material of cresol phosphate-based polyether polyol and melamine-based polyether polyol as a material substrate of a flame retardant, wherein the cresol phosphate-based polyether polyol contains a benzene ring structure, so that the mechanical property of the polyurethane foam product can be effectively improved, the contents of a molecular hard section and a molecular soft section are increased, the closed-cell rate of the polyurethane foam product is improved, a melamine derivative in the melamine-based polyether polyol has good thermal stability, the fire resistance of the polyurethane foam product is improved, two alcohol substrate materials are mixed by adopting aluminum hydroxide, the flame-retardant property of the surface of the polyurethane foam product material is improved, aluminum hydroxide forms a film-shaped structure on the surface of the material, the interior of the polyurethane foam product material can be insulated while flame-retardant, and the heat conductivity coefficient and the water absorption rate of the polyurethane foam product material are reduced, is more suitable for product heat preservation.)

1. The flame-retardant polyether material for the polyurethane foaming product is characterized in that: the flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 20-35 parts of phosphoric acid cresol fat-based polyol, 20-35 parts of melamine, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin, 0-10 parts of catalyst, 0-10 parts of propylene oxide and 10-20 parts of aluminum hydroxide.

2. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the phosphoric acid cresol fat-based polyol is obtained by mixing triphenylmethyl phosphate and diethanol amine and then carrying out reduced pressure distillation in a formaldehyde water solution environment with the concentration of over 37 percent, and the moisture content in the phosphoric acid cresol fat-based polyol is less than 0.05 percent.

3. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the phosphoric acid cresol fat-based polyol, the methanol and the formaldehyde are used as initiators, and the phosphoric acid cresol fat-based polyether polyol is obtained by adding polyolefin and a catalyst and reacting.

4. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the viscosity of the cresol phosphate ester-based polyol at 25 ℃ is 2000-3500 MPa.s, the hydroxyl value content (KOH) of the cresol phosphate ester-based polyol is 20-35mg/g, the pH value of the cresol phosphate ester-based polyol is 7.0-8.5, the acid value is 0.10-0.16, and the solid content is 30.7%.

5. The flame-retardant polyether material for polyurethane foam products as claimed in claim 3, wherein: the charging ratio of the cresol phosphate-based polyether polyol to the polyolefin during the reaction is 1: 0.5.

6. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA.

7. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the phosphoric acid cresol fat-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.

8. A method for preparing the flame-retardant polyether material for polyurethane foam products as claimed in claim 1, which is characterized in that: the method comprises the following steps:

s1, adding trityl phosphate and diethanol amine into a reaction container, stirring uniformly under the protection of nitrogen, heating, adding 37% of formaldehyde aqueous solution, refluxing for 3 hours, and then carrying out reduced pressure distillation to obtain the cresol phosphate ester-based polyol with the moisture of less than 1%;

s2, adding 20-35 parts of cresol phosphate ester-based polyol, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, and heating the reaction kettle to 120 ℃ for reaction for 3 hours;

s3, reducing the pressure of the reaction kettle, introducing 0.1MPa nitrogen when the pressure in the reaction kettle is reduced to 0MPa, cooling to 100 ℃, preserving the temperature for 2 hours, and dehydrating and catalyzing to obtain the cresol phosphate-based polyether polyol;

s4, adding 20-35 parts of melamine, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, uniformly stirring in a nitrogen environment, and heating the reaction kettle to 150 ℃ for reaction for 5 hours;

s5, reducing the pressure of the reaction kettle, and removing water and the catalyst in the reaction kettle to obtain melamine polyether polyol when the pressure in the reaction kettle is reduced to 0 MPa;

s6, adding the cresol phosphate-based polyether polyol and the melamine-based polyether polyol into a reaction kettle, uniformly stirring in a nitrogen environment, heating to 150 ℃, then adding 10-20 parts of aluminum hydroxide and 0-10 parts of catalyst, uniformly stirring, then reducing the pressure of the reaction kettle, and when the pressure in the reaction kettle is reduced to 0MPa, removing the water and the catalyst in the reaction kettle to obtain the finished flame-retardant polyether material.

9. The method for preparing the flame-retardant polyether material for the polyurethane foam product according to claim 8, wherein the method comprises the following steps: the addition ratio of the cresol phosphate fat-based polyether polyol to the melamine polyether polyol to the aluminum hydroxide is 1:1: 0.5-1.5.

Technical Field

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

Background

The polyurethane rigid foam is a high molecular polymer which is prepared by mixing isocyanate and polyether serving as main raw materials through a special device under the action of various auxiliary agents such as a foaming agent, a catalyst, a flame retardant and the like and spraying the mixture at high pressure to foam on site, is suitable for sofa furniture, pillows, cushions, toys, clothes, sound insulation linings and the like, is sometimes suitable for the fields of pipe-channel heat insulation, building heat insulation, cold storage heat insulation and the like due to low heat conductivity coefficient and good waterproof performance, most of the conventional flame-retardant polyether materials for polyurethane foam products adopt polyether polyol formed by white polyether or glycerol and epoxide, although the materials have good water resistance and impact resistance, the polyether polyol formed by the glycerol and the epoxide contains a large amount of active hydrogen, and is not beneficial to reducing the closed-cell rate of the polyurethane foam products in the using process, thereby reducing the production quality of the polyurethane foam products, the polyurethane foam product has poor thermal insulation performance.

Disclosure of Invention

The invention aims to provide a flame-retardant polyether material for a polyurethane foaming product, which can improve the closed cell rate of the polyurethane foaming product, preserve the heat of the interior of the polyurethane foaming product material while resisting flame, reduce the heat conductivity coefficient and the water absorption of the polyurethane foaming product material, and is more suitable for product heat preservation, so as to solve the problems that polyether polyol formed by glycerol and epoxide, which is proposed in the background technology, contains a large amount of active hydrogen, and is not beneficial to reducing the closed cell rate of the polyurethane foaming product in the using process, so that the production quality of the polyurethane foaming product is reduced, and the heat preservation performance of the polyurethane foaming product is poor.

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

the flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 20-35 parts of phosphoric acid cresol fat-based polyol, 20-35 parts of melamine, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin, 0-10 parts of catalyst, 0-10 parts of propylene oxide and 10-20 parts of aluminum hydroxide.

Preferably, the cresyl phosphate polyol is obtained by mixing trityl phosphate and diethanol amine and then carrying out vacuum distillation in a 37% formaldehyde aqueous solution environment, wherein the moisture content in the cresyl phosphate polyol is less than 0.05%.

Preferably, the cresol phosphate based polyol, the methanol and the formaldehyde are used as initiators, and the cresol phosphate based polyol, the methanol and the formaldehyde are added with the polyolefin and the catalyst to react to obtain the cresol phosphate based polyether polyol.

Preferably, the viscosity of the cresol phosphate ester-based polyol at 25 ℃ is 2000-3500 MPa.s, the hydroxyl value content (KOH) of the cresol phosphate ester-based polyol is 20-35mg/g, the pH value of the cresol phosphate ester-based polyol is 7.0-8.5, the acid value is 0.10-0.16, and the solid content is 30.7%.

Preferably, the feeding ratio of the cresol phosphate-based polyether polyol to the polyolefin in the reaction is 1: 0.5.

Preferably, the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA.

Preferably, the cresol phosphate ester-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.

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

s1, adding trityl phosphate and diethanol amine into a reaction container, stirring uniformly under the protection of nitrogen, heating, adding 37% of formaldehyde aqueous solution, refluxing for 3 hours, and then carrying out reduced pressure distillation to obtain the cresol phosphate ester-based polyol with the moisture of less than 1%;

s2, adding 20-35 parts of cresol phosphate ester-based polyol, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, and heating the reaction kettle to 120 ℃ for reaction for 3 hours;

s3, reducing the pressure of the reaction kettle, introducing 0.1MPa nitrogen when the pressure in the reaction kettle is reduced to 0MPa, cooling to 100 ℃, preserving the temperature for 2 hours, and dehydrating and catalyzing to obtain the cresol phosphate-based polyether polyol;

s4, adding 20-35 parts of melamine, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, uniformly stirring in a nitrogen environment, and heating the reaction kettle to 150 ℃ for reaction for 5 hours;

s5, reducing the pressure of the reaction kettle, and removing water and the catalyst in the reaction kettle to obtain melamine polyether polyol when the pressure in the reaction kettle is reduced to 0 MPa;

s6, adding the cresol phosphate-based polyether polyol and the melamine-based polyether polyol into a reaction kettle, uniformly stirring in a nitrogen environment, heating to 150 ℃, then adding 10-20 parts of aluminum hydroxide and 0-10 parts of catalyst, uniformly stirring, then reducing the pressure of the reaction kettle, and when the pressure in the reaction kettle is reduced to 0MPa, removing the water and the catalyst in the reaction kettle to obtain the finished flame-retardant polyether material.

Preferably, the addition ratio of the cresol phosphate-based polyether polyol to the melamine-based polyether polyol to the aluminum hydroxide is 1:1: 0.5-1.5.

The invention provides a flame-retardant polyether material for polyurethane foam products, which uses a mixed material of cresol phosphate-based polyether polyol and melamine-based polyether polyol as a material substrate of a flame retardant, wherein the cresol phosphate-based polyether polyol contains a benzene ring structure, so that the mechanical property of the polyurethane foam product can be effectively improved, the contents of a molecular hard section and a molecular soft section are increased, the closed-cell rate of the polyurethane foam product is improved, a melamine derivative in the melamine-based polyether polyol has good thermal stability, the fire resistance of the polyurethane foam product is improved, two alcohol substrate materials are mixed by adopting aluminum hydroxide, the flame-retardant property of the surface of the polyurethane foam product material is improved, the aluminum hydroxide forms a film-shaped structure on the surface of the material, the interior of the polyurethane foam product material can be insulated while flame-retardant, and the heat conductivity coefficient and the water absorption rate of the polyurethane foam product material are reduced, is more suitable for product heat preservation.

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.