阅读说明：本技术 添加醇胺的阻燃聚醚多元醇及其制备方法 (Add the flame retardant polyether polyol and preparation method thereof of hydramine ) 是由 江学良 陈明轩 姚楚 游峰 姚军龙 刘仿军 于 2019-08-30 设计创作，主要内容包括：本发明属于有机合成领域,具体涉及添加醇胺的阻燃聚醚多元醇及其合成方法。本发明以醇胺和二氯化磷酸苯酯为起始原料,经两步反应制备出阻燃聚醚多元醇,反应收率高达90％,且反应过程简单、反应条件温和、易于控制；并且本制备方法所制备的阻燃聚醚多元醇,具有中等黏度,与其他多元醇具有良好的相容性和持久的阻燃性,具有较大的社会经济效益。(The invention belongs to organic synthesis fields, and in particular to add the flame retardant polyether polyol and its synthetic method of hydramine.The present invention prepares flame retardant polyether polyol using hydramine and PhosphorodichloridicAcid Acid Phenyl Ester as starting material, through two-step reaction, and reaction yield is up to 90%, and reaction process is simple, reaction condition is mild, easily controllable；And flame retardant polyether polyol prepared by this preparation method has midium-viscosity, has good compatibility and lasting anti-flammability with other polyalcohols, has biggish economic results in society.)

1. a kind of preparation method for the flame retardant polyether polyol for adding hydramine, which comprises the steps of:

(1) hydramine and triethylamine are added in organic solvent, heating up and stirring to all dissolutions obtains mixed liquor a；

(2) it is poured into three-necked flask after PhosphorodichloridicAcid Acid Phenyl Ester being dissolved in organic solvent；

(3) it stirs at a certain temperature and is slowly dropped to mixed liquor a in three-necked flask by dropping funel, after being added dropwise to complete By reaction, temperature reaction obtains product b under nitrogen protection；

(4) product b is obtained into flame retardant polyether polyol product by vacuum distillation removal organic solvent.

2. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the hydramine is diethanol Amine, N methyldiethanol amine, N butyl diethanol amine or N, N- dihydroxy ethyl-para-totuidine.

3. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the hydramine and triethylamine rub You are than being 6:1 ~ 8:1.

4. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the PhosphorodichloridicAcid Acid Phenyl Ester Molar ratio with hydramine is 1:0.8 ~ 1:1.

5. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the organic solvent is Isosorbide-5-Nitrae- Dioxane.

6. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that stirred described in step (3) The temperature that mixed liquor a is added dropwise is 25 DEG C ~ 35 DEG C, and the temperature of the reaction is 58 DEG C ~ 78 DEG C, and the reaction time is 5h ~ 8h.

7. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the vacuum distillation temperature is 58℃~78℃。

8. any preparation method of claim 1 ~ 7 prepares obtained flame-retardant polyether polyol product.

Technical field

The invention belongs to organic synthesis fields, and in particular to the flame retardant polyether polyol of addition hydramine and its preparation side Method.

Background technique

Fire retardant, assigns the functional aid of combustible polymers flame retardancy, and fire-retardant primarily directed to high molecular material sets Meter；There are many types for fire retardant, are divided into additive flame retardant and reactive flame retardant by application method.

Additive flame retardant is added in polymer by mechanical mix techniques, and polymer is made to have anti-flammability, mesh The main organic fire-retardant of preceding additive flame retardant and inorganic fire retardants, halogenated flame retardant and non-halogen.Organic is with bromine system, phosphorus nitrogen System, nitrogen system and red phosphorus and compound are some fire retardants of representative, inorganic mainly antimony oxide, magnesium hydroxide, hydroxide Aluminium, the flame-retardant systems such as silicon systems.

Reactive flame retardant is then to participate in polymerization reaction as a kind of monomer, therefore make polymer itself to contain flame-retardant composition , its advantage is that smaller on the influence of polymer material service performance, anti-flammability is lasting.Common reactive flame retardant is to pass through fluorine The ignition-proof elements such as chlorine bromine iodine realize flame retardant effect, but the burning of this reactive flame retardant can generate harmful substance, Bu Nengman Demand of the sufficient material at environmentally protective aspect, and the preparation process of this reactive flame retardant often complicated cumbersome, operation difficulty Greatly.Therefore, the preparation method for studying the small reactive flame retardant of environmentally protective one kind, simple process, operation difficulty becomes the general trend of events Become.

Summary of the invention

The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide the flame retardant polyether polyol and its system of addition hydramine Preparation Method.

For achieving the above object, the technical scheme adopted by the invention is as follows:

The flame retardant polyether polyol for adding hydramine, includes the following steps:

(1) hydramine and triethylamine are added in organic solvent, heating up and stirring to all dissolutions obtains mixed liquor a；

(2) it is poured into three-necked flask after PhosphorodichloridicAcid Acid Phenyl Ester being dissolved in organic solvent；

(3) it stirs at a certain temperature and is slowly dropped to mixed liquor a in three-necked flask by dropping funel, drip By reaction, temperature reaction obtains product b under nitrogen protection after；

(4) product b is obtained into flame retardant polyether polyol product by vacuum distillation removal organic solvent.

In above scheme, the hydramine and triethylamine molar ratio are 6:1~8:1.

In above scheme, the molar ratio of the PhosphorodichloridicAcid Acid Phenyl Ester and hydramine is 1:0.8~1:1.

In above scheme, the organic solvent is Isosorbide-5-Nitrae-dioxane.

In above scheme, the temperature of agitation and dropping mixed liquor a described in step (3) is 25~35 DEG C, the temperature of the reaction Degree is 58~78 DEG C, and the reaction time is 5~8h.

In above scheme, the vacuum distillation temperature is 58~78 DEG C.

Above-mentioned preparation method prepares obtained flame-retardant polyether polyol product.

Beneficial effects of the present invention: the present invention is using hydramine and PhosphorodichloridicAcid Acid Phenyl Ester as starting material, through two-step reaction system Standby flame retardant polyether polyol out, reaction yield is up to 90%, and reaction process is simple, reaction condition is mild, easily controllable；And Flame retardant polyether polyol prepared by this preparation method has midium-viscosity, has good compatibility with other polyalcohols, with The resistance combustion polyurethane foam that expanded graphite packing is prepared jointly has the anti-flammability of high-efficient and lasting, has biggish social economy effect Benefit.

Detailed description of the invention

Fig. 1 is Examples 1 to 5 synthesis flame retardant polyether polyol and then the limit oxygen index for preparing flame retarded polyurethane-foam Coefficient.

Specific embodiment

For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention Content is not limited solely to the following examples.