CN110527079B

CN110527079B - Fire-retardant polyether polyol added with alcohol amine and preparation method thereof

Info

Publication number: CN110527079B
Application number: CN201910815886.8A
Authority: CN
Inventors: 江学良; 陈明轩; 姚楚; 游峰; 姚军龙; 刘仿军
Original assignee: Wuhan Institute of Technology
Current assignee: Wuhan Institute of Technology
Priority date: 2019-08-30
Filing date: 2019-08-30
Publication date: 2022-12-06
Anticipated expiration: 2039-08-30
Also published as: CN110527079A

Abstract

The invention belongs to the field of organic synthesis, and particularly relates to flame-retardant polyether polyol added with alcohol amine and a synthesis method thereof. The invention takes the alcohol amine and the phenyl dichlorophosphate as the initial raw materials to prepare the flame-retardant polyether polyol through two-step reaction, the reaction yield reaches up to 90 percent, and the reaction process is simple, the reaction condition is mild and easy to control; the flame-retardant polyether polyol prepared by the preparation method has medium viscosity, good compatibility with other polyols, durable flame retardance and great social and economic benefits.

Description

Fire-retardant polyether polyol added with alcohol amine and preparation method thereof

Technical Field

The invention belongs to the field of organic synthesis, and particularly relates to flame-retardant polyether polyol added with alcohol amine and a preparation method thereof.

Background

The flame retardant is a functional auxiliary agent for endowing the inflammable polymer with flame retardancy, and is mainly designed aiming at the flame retardancy of a high polymer material; the flame retardants are of various types, and are classified into additive type flame retardants and reactive type flame retardants according to the method of use.

The additive flame retardant is added into the polymer by a mechanical mixing method to enable the polymer to have flame retardance, and at present, the additive flame retardant mainly comprises an organic flame retardant, an inorganic flame retardant, a halogen flame retardant and a non-halogen flame retardant. Organic flame retardants are represented by bromine, phosphorus-nitrogen, red phosphorus and compounds, and inorganic flame retardants are mainly flame retardant systems such as antimony trioxide, magnesium hydroxide, aluminum hydroxide, silicon and the like.

The reactive flame retardant is used as a monomer to participate in polymerization reaction, so that the polymer contains a flame retardant component, and the reactive flame retardant has the advantages of less influence on the service performance of a polymer material and lasting flame retardance. The common reactive flame retardant realizes the flame retardant effect through flame retardant elements such as fluorine, chlorine, bromine, iodine and the like, but the combustion of the reactive flame retardant can generate harmful substances, the requirements of materials on the aspects of green and environmental protection cannot be met, and the preparation process of the reactive flame retardant is complex and complicated and has high operation difficulty. Therefore, the research on a preparation method of the reaction type flame retardant which is environment-friendly, simple in process and low in operation difficulty is in the trend.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the flame-retardant polyether polyol added with alcohol amine and the preparation method thereof.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:

the flame-retardant polyether polyol added with alcohol amine comprises the following steps:

(1) Adding alcohol amine and triethylamine into an organic solvent, heating and stirring until all the alcohol amine and the triethylamine are dissolved to obtain a mixed solution a;

(2) Dissolving phenyl dichlorophosphate in an organic solvent, and pouring into a three-neck flask;

(3) Stirring at a certain temperature, slowly dropwise adding the mixed solution a into a three-neck flask through a dropping funnel, and heating the reaction under the protection of nitrogen after dropwise adding to obtain a product b;

(4) And (4) removing the organic solvent from the product b through reduced pressure distillation to obtain the flame-retardant polyether polyol product.

In the scheme, the molar ratio of the alcohol amine to the triethylamine is 6:1 to 8:1.

in the scheme, the molar ratio of phenyl dichlorophosphate to alcohol amine is 1:0.8 to 1:1.

in the scheme, the organic solvent is 1,4-dioxane.

In the scheme, the temperature of the mixed solution a dropwise added in the step (3) is 25-35 ℃, the reaction temperature is 58-78 ℃, and the reaction time is 5-8 h.

In the scheme, the reduced pressure distillation temperature is 58-78 ℃.

The flame-retardant polyether polyol product prepared by the preparation method.

The invention has the beneficial effects that: the invention takes the alcohol amine and the phenyl dichlorophosphate as the initial raw materials to prepare the flame-retardant polyether polyol through two-step reaction, the reaction yield reaches up to 90 percent, and the reaction process is simple, the reaction condition is mild and easy to control; the flame-retardant polyether polyol prepared by the preparation method has medium viscosity, has good compatibility with other polyols, and has high-efficiency and durable flame retardance and larger social and economic benefits when being prepared together with the expanded graphite filler.

Drawings

FIG. 1 is the limiting oxygen index coefficient for the synthesis of flame retardant polyether polyols of examples 1-5 to produce flame retardant polyurethane foams.

Detailed Description

In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.

Example 1

A flame retardant polyether polyol is synthesized by the following steps:

(1) Adding 28g of diethanolamine and 2g of triethylamine into 115ml of 1, 4-dioxane, heating to 28 ℃, and stirring until the diethanolamine and the triethylamine are completely dissolved to obtain a mixed solution a;

(2) Dissolving 20g of phenyl dichlorophosphate in 110ml of 1,4-dioxane, heating to 25 ℃, stirring until all the phenyl dichlorophosphate is dissolved, pouring the mixture into a three-neck flask, and keeping the temperature for 25min;

(3) Slowly dropwise adding the mixed solution a into a three-neck flask through a dropping funnel under the protection of nitrogen and under the stirring condition of 30 ℃, and after dropwise adding is finished, heating the three-neck flask in a 65 ℃ water bath, heating and mechanically stirring for 6 hours to obtain a product b;

(4) And removing unreacted components and the organic solvent from the product b by reduced pressure distillation (the reduced pressure distillation temperature is 60 ℃) to obtain the flame-retardant polyether polyol product.

The hydroxyl value is measured to be 33mg KOH/g by adopting an acetylation method, and the yield is 91 percent; the limit oxygen index of polyurethane foam prepared by adding 10g of expandable graphite into 50g of flame-retardant polyether polyol product and then reacting with isocyanate is 31.2, and the vertical combustion test reaches V-0 grade.

Example 2

A flame retardant polyether polyol is synthesized by the following steps:

(1) Adding 28g N-methyldiethanolamine and 2g triethylamine into 130ml 1, 4-dioxane, heating to 34 ℃, and stirring until all the materials are dissolved to obtain a mixed solution a;

(2) Dissolving 20g of phenyl dichlorophosphate in 110ml of 1,4-dioxane, heating to 27 ℃, stirring until all the phenyl dichlorophosphate is dissolved, pouring the mixture into a three-neck flask, and preserving the temperature for 32min;

(3) Slowly dropwise adding the mixed solution a into a three-neck flask through a dropping funnel under the protection of nitrogen and under the stirring condition of 30 ℃, and after dropwise adding is finished, heating the three-neck flask in a 65 ℃ water bath, heating and mechanically stirring for 7 hours to obtain a product b;

(4) And removing unreacted components and the organic solvent from the product b by reduced pressure distillation (the reduced pressure distillation temperature is 71 ℃) to obtain the flame-retardant polyether polyol product.

The hydroxyl value is determined to be 34mg KOH/g by adopting an acetylation method, and the yield is 91 percent; the limit oxygen index of polyurethane foam prepared by adding 10g of expandable graphite into 50g of flame-retardant polyether polyol product and then reacting with isocyanate is 31.0, and the vertical combustion test reaches V-0 grade.

Example 3

A flame retardant polyether polyol is synthesized by the following steps:

(1) Adding 24g N-butyldiethanolamine and 2g triethylamine into 110ml 1, 4-dioxane, heating to 25 ℃, and stirring until all the materials are dissolved to obtain a mixed solution a;

(2) Dissolving 17g of phenyl dichlorophosphate in 105ml of 1,4-dioxane, heating to 25 ℃, stirring until all the phenyl dichlorophosphate is dissolved, pouring the mixture into a three-neck flask, and preserving the temperature for 30min;

(3) Slowly dropwise adding the mixed solution a into a three-neck flask through a dropping funnel under the protection of nitrogen and under the stirring condition of 31 ℃, and after dropwise adding is finished, heating the three-neck flask in a 72 ℃ water bath, heating and mechanically stirring for 5.5 hours to obtain a product b;

(4) And removing unreacted components and the organic solvent from the product b by reduced pressure distillation (the reduced pressure distillation temperature is 65 ℃) to obtain the flame-retardant polyether polyol product.

The hydroxyl value is determined to be 34mg KOH/g by adopting an acetylation method, and the yield is 95 percent; the limit oxygen index of polyurethane foam prepared by adding 10g of expandable graphite into 50g of flame-retardant polyether polyol product and then reacting with isocyanate is 33.4, and the vertical combustion test reaches V-0 grade.

Example 4

A flame retardant polyether polyol is synthesized by the following steps:

(1) 23gN, N-dihydroxyethyl-p-toluidine and 3.3g triethylamine are added into 100ml 1, 4-dioxane, heated to 31 ℃ and stirred until all the components are dissolved to obtain a mixed solution a;

(2) Dissolving 20g of phenyl dichlorophosphate in 105ml of 1,4-dioxane, heating to 26 ℃, stirring until all the phenyl dichlorophosphate is dissolved, pouring the mixture into a three-neck flask, and preserving the temperature for 23min;

(3) Slowly dropwise adding the mixed solution a into a three-neck flask through a dropping funnel under the protection of nitrogen and under the stirring condition of 34 ℃, and after dropwise adding is finished, heating the three-neck flask in 29 ℃ water bath, heating and mechanically stirring for 7 hours to obtain a product b;

(4) And removing unreacted components and the organic solvent from the product b by reduced pressure distillation (the reduced pressure distillation temperature is 58 ℃) to obtain the flame-retardant polyether polyol product.

The hydroxyl value is measured to be 36mg KOH/g by adopting an acetylation method, and the yield is 91 percent; the limit oxygen index of polyurethane foam prepared by adding 10g of expandable graphite into 50g of flame-retardant polyether polyol product and then reacting with isocyanate is 31.8, and the vertical combustion test reaches V-0 grade.

TABLE 1 Performance indices of flame-retardant polyether polyols

Performance index	Example 1	Example 2	Example 3	Example 4
					Hydroxyl value MgKOH/g	33	34	34	36
Yield of	91％	91％	95％	91％

It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims

1. The preparation method of the flame-retardant polyether polyol added with the alcohol amine is characterized by comprising the following steps:

(1) Adding alcohol amine and triethylamine into an organic solvent, heating and stirring until the alcohol amine and the triethylamine are completely dissolved to obtain a mixed solution a;

the alcohol amine is diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine or N, N-dihydroxyethyl-

P-toluidine; the molar ratio of the alcohol amine to the triethylamine is 6:1~8:1; the organic solvent is 1,4-dioxane;

(2) Dissolving phenyl dichlorophosphate in an organic solvent, and pouring into a three-neck flask; said phosphorus dichloride benzene

The molar ratio of ester to alcohol amine is 1:0.8 to 1:1; the organic solvent is 1,4-dioxane;

(3) Stirring at a certain temperature, slowly dripping the mixed solution a into a three-neck flask through a dropping funnel, and dripping

After the addition is finished, heating the reaction under the protection of nitrogen to react to obtain a product b; the temperature of the mixed solution a is stirred and dripped

The temperature is 25-35 ℃, the reaction temperature is 58-78 ℃, and the reaction time is 5-8h;

2. The method of claim 1, wherein the reduced pressure steaming is carried out to produce the flame retardant polyether polyol

The distillation temperature is 58-78 ℃.