阅读说明：本技术 一种反应型阻燃聚醚多元醇及其制备方法 (Reactive flame-retardant polyether polyol and preparation method thereof ) 是由 李学庆 黄丹丹 刘强 王台 于 2019-11-25 设计创作，主要内容包括：本申请涉及一种反应型阻燃聚醚多元醇的制备方法,其包括在反应温度为90～155℃,反应压力不超过0.60MPa的条件下,且于存在催化剂时,使含卤起始剂与氧化烯烃反应预定时间段,得到所述反应型阻燃聚醚多元醇。本申请还涉及利用上述方法制备的反应型阻燃聚醚多元醇。本申请还涉及反应型阻燃聚醚多元醇作为阻燃剂在制备聚氨酯泡沫中的应用。本申请的阻燃聚醚多元醇具有粘度较高、官能度较低、反应活性高等优势,且该阻燃聚醚多元醇制备的硬质泡沫塑料聚氨酯具有强度高、尺寸稳定性好、导热系数低、粘结力强、永久阻燃等特点,广泛适用于生产高阻燃喷涂、板材等聚氨酯泡沫。(The application relates to a preparation method of reactive flame-retardant polyether polyol, which comprises the step of reacting a halogen-containing initiator with an alkylene oxide for a preset time period in the presence of a catalyst under the conditions that the reaction temperature is 90-155 ℃ and the reaction pressure is not more than 0.60MPa to obtain the reactive flame-retardant polyether polyol. The application also relates to reactive flame retardant polyether polyols prepared by the above process. The application also relates to the use of the reactive flame retardant polyether polyol as a flame retardant in the preparation of polyurethane foams. The flame-retardant polyether polyol has the advantages of high viscosity, low functionality, high reaction activity and the like, and the rigid foam plastic polyurethane prepared from the flame-retardant polyether polyol has the characteristics of high strength, good dimensional stability, low heat conductivity coefficient, strong binding power, permanent flame retardance and the like, and is widely applicable to production of polyurethane foams such as high-flame-retardant spraying and plates.)

1. The preparation method of the reactive flame-retardant polyether polyol is characterized by comprising the step of reacting a halogen-containing initiator with an alkylene oxide for a preset time period in the presence of a catalyst under the conditions that the reaction temperature is 90-155 ℃ and the reaction pressure is not more than 0.60MPa to obtain the reactive flame-retardant polyether polyol.

2. The method of claim 1, wherein the molar ratio of the halogen-containing initiator to the alkylene oxide is from 1:4 to 10.

3. The method of preparing a reactive flame retardant polyether polyol according to claim 1, wherein the halogen-containing initiator comprises a bromine-containing initiator, preferably the halogen-containing initiator comprises tetrabromophthalic anhydride, tetrabromobisphenol a, tribromophenol;

the alkylene oxide comprises ethylene oxide and/or propylene oxide;

the catalyst is a base catalyst, which preferably comprises one or more of the following: potassium hydroxide, sodium hydroxide, potassium methoxide, and sodium methoxide.

4. The method of claim 1, wherein the catalyst is used in an amount of 1.3% by mass based on the total mass of the halogen-containing initiator, the alkylene oxide and the catalyst.

5. A method according to any of claims 1-4, characterized in that the method is carried out according to the following steps:

adding a halogen-containing initiator and an alkaline catalyst into a reaction kettle, mixing, introducing an inert gas, alternately replacing at least two times under positive pressure and negative pressure, starting stirring under negative pressure, and heating to 90-100 ℃;

quickly adding a first part of the olefin oxide into the reaction kettle, controlling the reaction temperature to be 90-110 ℃, and carrying out polymerization reaction under the reaction pressure of not more than 0.30MPa, wherein the first part of the olefin oxide accounts for 3% of the total amount of the olefin oxide;

adding a second part of the olefin oxide in a continuous feeding mode or a batch feeding mode, and carrying out polymerization reaction at the temperature of 90-155 ℃ and the reaction pressure of not more than 0.60MPa, wherein when batch feeding is adopted, the feeding amount of each batch is 6-10% of the total amount of the second part of the olefin oxide;

maintaining the reaction temperature within the range of 90-155 ℃ for curing until the pressure is not changed any more.

6. The method of claim 5, wherein after the halogen-containing initiator and the base catalyst are added into the reaction kettle, inert gas is introduced, and the system is alternately replaced at least twice by positive pressure and negative pressure so as to ensure anhydrous and oxygen-free reaction conditions of the system.

7. The process of claim 5 wherein said first portion of propylene oxide is pre-dripped prior to feeding and continues to said second portion of alkylene oxide as the temperature increases and the pressure decreases.

8. The method of claim 5, wherein the aging process is divided into two parts, the temperature of the first 2-hour aging is controlled within the range of 90-135 ℃, and the temperature of the second 2-hour aging is controlled within the range of 135-155 ℃.

9. A reactive flame retardant polyether polyol prepared by the process as claimed in claims 1-8.

10. The reactive flame retardant polyether polyol of claim 9, wherein the reactive flame retardant polyether polyol has a number average molecular weight of 400 to 1000.

11. Use of the reactive flame retardant polyether polyol of claim 10 as a flame retardant in the synthesis of polyurethane foams.

Technical Field

The application relates to the technical field of chemical synthesis, in particular to reactive flame-retardant polyether polyol and a preparation method thereof, which can be applied to the industries of producing polyurethane foams such as high flame-retardant spraying, plates and the like.

Background

Like most other high molecular materials, polyurethane is not flame-retardant, and generates toxic gas when burning, thus endangering personal and property safety. In particular, polyurethane foam has small density, large specific surface area, high open area ratio of polyurethane flexible foam, more combustible components, and high air circulation during combustion, thereby continuously providing oxygen, being flammable and not easy to self-extinguish. Therefore, polyurethane articles, particularly polyurethane foams, are generally given a certain flame retardancy by various methods. The addition of flame retardants is the most common method, which is an important adjuvant for polyurethane foams.

The flame retardant has various varieties, and includes solid powder flame retardants and liquid flame retardants in forms; from the chemical property, inorganic flame retardant and organic flame retardant exist; the chemical components include halogenated phosphate, halogenated organic matter, melamine, ammonium polyphosphate, aluminum hydroxide and other flame retardants; from the chemical reaction type, there are additive type non-reactive flame retardants and reactive flame retardants represented by flame retardant polyols.

The reactive flame retardant used for polyurethane is mostly various liquid and solid flame retardant polyols containing phosphorus, nitrogen or (and) halogen, etc. The reactive flame retardant is used as a reaction component to participate in the reaction, so that the polyurethane contains the flame retardant component, and the reactive flame retardant has the characteristics of small influence on the performance of the material, stable flame retardant effect and the like.

For this reason, there is a strong need in the art for a reactive flame retardant polyether polyol and a method for preparing the same.

Disclosure of Invention

The present application aims to solve the above-mentioned technical problems of the prior art by providing a reactive flame-retardant polyether polyol which can be used as a flame retardant in the synthesis of polyurethane and simultaneously participate in the polyurethane synthesis reaction.

The application also provides a preparation method of the reactive flame-retardant polyether polyol.

It is also an object of the present application to provide the use of the polyether polyols as described above as flame retardants in the preparation of polyurethane foams.

In order to achieve the above object, the present application provides the following technical solutions.

In a first aspect, the present application provides a method for preparing a reactive flame-retardant polyether polyol, which is characterized in that the method comprises reacting a halogen-containing initiator with an alkylene oxide in the presence of a catalyst at a reaction temperature of 90 to 155 ℃ and a reaction pressure of not more than 0.60MPa for a predetermined period of time to obtain the reactive flame-retardant polyether polyol.

In one embodiment of the first aspect, the molar ratio of the halogen-containing initiator to the alkylene oxide is from 1:4 to 10.

In one embodiment of the first aspect, the halogen-containing initiator comprises a bromine-containing initiator, which preferably comprises tetrabromophthalic anhydride, tetrabromobisphenol a, tribromophenol, or the like;

the alkylene oxide comprises ethylene oxide and/or propylene oxide;

the catalyst is an alkali catalyst.

The base catalyst may include potassium hydroxide, sodium hydroxide, potassium methoxide, or sodium methoxide, etc.

In one embodiment of the first aspect, the catalyst is used in an amount of 1.3% by weight based on the total mass of the halogen-containing initiator, alkylene oxide and catalyst.

In one embodiment of the first aspect, the method is performed according to the following steps:

adding a halogen-containing initiator and an alkaline catalyst into a reaction kettle, mixing, introducing an inert gas, alternately replacing at least two times under positive pressure and negative pressure, starting stirring under negative pressure, and heating to 90-100 ℃;

quickly adding a first part of the olefin oxide into the reaction kettle, controlling the reaction temperature to be 90-110 ℃, and carrying out polymerization reaction under the reaction pressure of not more than 0.30MPa, wherein the first part of the olefin oxide accounts for 3% of the total amount of the olefin oxide;

adding a second part of the olefin oxide in a continuous feeding mode or a batch feeding mode, and carrying out polymerization reaction at the temperature of 90-155 ℃ and the reaction pressure of not more than 0.60MPa, wherein when batch feeding is adopted, the feeding amount of each batch is 6-10% of the total amount of the second part of the olefin oxide;

maintaining the reaction temperature within the range of 90-155 ℃ for curing until the pressure is not changed any more.

In one embodiment of the first aspect, after the halogen-containing initiator and the base catalyst are added to the reaction kettle, an inert gas is introduced, and the system is alternately replaced at least twice by positive and negative pressure so as to ensure anhydrous and oxygen-free reaction conditions of the system.

In one embodiment of the first aspect, the first portion of propylene oxide is pre-dripped before feeding and continues to the second portion of alkylene oxide as the temperature rises and the pressure drops.

In one embodiment of the first aspect, the aging process is divided into two parts, wherein the temperature of the first 2-hour aging is controlled within the range of 90-135 ℃, and the temperature of the second 2-hour aging is controlled within the range of 135-155 ℃.

In a second aspect, the present application provides a reactive flame retardant polyether polyol prepared by the method according to the first aspect.

In one embodiment of the second aspect, the reactive flame retardant polyether polyol has a number average molecular weight of 400 to 1000.

In a third aspect, the present application provides a use of a reactive flame retardant polyether polyol as described in the second aspect as a flame retardant in the synthesis of a polyurethane foam.

Compared with the prior art, the preparation method has the positive effects that (1) the preparation method of the flame-retardant polyether polyol comprises the following steps: the method is simple, the production period is short, the process operation is simple, the production cost is low, the prepared flame-retardant polyether is easy to dissolve in water, the hydroxyl value and the viscosity are adjustable, the stability is good, and different customer requirements can be met. (2) The halogen-containing reaction type flame-retardant polyether polyol prepared by the method has the advantages of moderate viscosity, high reaction activity and the like, and the prepared polyurethane foam plastic has the characteristics of high strength, good dimensional stability, low heat conductivity coefficient, strong binding power, permanent flame retardance and the like. It is widely applicable to the polyurethane foam industries of producing high flame-retardant spraying, plates and the like.

Detailed Description

Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.

The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.

When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.

The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.

In a specific embodiment, the application provides a preparation method of a halogen-containing reactive flame-retardant polyether polyol, which comprises the steps of gradually introducing propylene oxide into a halogen-containing initiator and 1.3% of an alkali catalyst in the total mass under the conditions that the reaction temperature is 90-155 ℃ and the reaction pressure is not more than 0.60MPa, so that ring-opening polymerization reaction is carried out on the propylene oxide, and the halogen-containing reactive flame-retardant polyether polyol is prepared; wherein the molar ratio of the halogen-containing initiator to the propylene oxide is 1: 4-10.

In some embodiments, the halogen-containing initiator may also include other corresponding compositions not limited to elemental bromine, elemental chlorine, and elemental phosphorus.

In a preferred embodiment, the halogen-containing initiator comprises tetrabromophthalic anhydride, tetrabromobisphenol A, tribromophenol.

In some embodiments, the reactive flame retardant polyether polyol prepared with a halogen-containing initiator has a number average molecular weight of 400 to 1000.

In some embodiments, the process for preparing a halogen-containing starter is carried out according to the following steps:

(1) adding a halogen-containing initiator and an alkaline catalyst into a reaction kettle, mixing, introducing inert gas, alternately replacing at least two times under positive pressure and negative pressure, starting stirring under negative pressure, and heating to 90-100 ℃;

(2) heating is suspended, a first part of olefin oxide is rapidly added into the reaction kettle, and the reaction temperature is controlled to be 90-110 ℃, wherein the first part of olefin oxide accounts for 3% of the total amount of the olefin oxide;

(3) adding a second part of olefin oxide in a continuous feeding or batch feeding manner, and carrying out polymerization reaction at the temperature of 90-155 ℃ and under the reaction pressure of not more than 0.60MPa, wherein when batch feeding is adopted, the feeding amount of each batch is 6-10% of the total amount of the propylene oxide;

(4) maintaining the reaction temperature within the range of 90-155 ℃ for curing until the pressure is not changed;

in some embodiments, after the halogen-containing initiator and the base catalyst are added into the reaction kettle, inert gas is introduced, and is alternately replaced at least twice by positive pressure and negative pressure to ensure the anhydrous and anaerobic reaction conditions of the system, and finally, under the condition of negative pressure, for example, -0.90MPa, stirring is started and heating is carried out to 90-100 ℃. In some embodiments, the inert gas may be nitrogen or argon.

In some embodiments, the heating is stopped and a first portion of the alkylene oxide is rapidly added to the kettle after the temperature of the mixture of halogen-containing initiator and base catalyst reaches about 90 ℃. The first part of propylene oxide is pre-dripped before feeding, feeding is suspended when the pressure in the reaction kettle reaches positive pressure, the reaction condition is observed, when the temperature rises and the pressure drops, the material starts to react, the alkylene oxide is continuously fed, and the reaction temperature is controlled to be 90-100 ℃.

In some embodiments, after the temperature reaches 100 ℃, propylene oxide is continuously added, the propylene oxide is slowly fed in the early stage, the temperature is raised by using the reaction heat, and the reaction temperature is controlled to be 90-155 ℃. And starting the external circulating pump after the feeding is finished. The temperature is raised by the reaction heat of the materials as much as possible, and heating is not needed, so that local overheating is prevented, and the color depth is prevented. In the reaction process of the materials, the pressure is not more than 0.60 MPa.

In some embodiments, the reaction temperature is maintained for maturation until the pressure will not be. In the process, the curing process is divided into two parts: the temperature of the early-stage 2-hour curing is controlled within the range of 90-135 ℃, the temperature of the later-stage curing is controlled within the range of 135-155 ℃, and finally, the temperature is reduced to 80 ℃ for discharging after the final product is qualified.

In a preferred embodiment, the process for preparing a reactive flame-retardant polyether polyol from a halogen-containing initiator and a base catalyst comprises the steps of:

(1) adding halogen-containing initiator accounting for 60%, 50% and 40% of the total mass into a reactor, adding alkali catalyst accounting for 1.3% of the total mass of reactants into a reaction vessel, introducing inert gas, and alternately replacing at least twice through positive pressure and negative pressure to ensure the anhydrous and anaerobic reaction conditions of the system, finally, under the condition of negative pressure, starting stirring and heating to 90-100 ℃, stopping heating after reaching about 90 ℃, and starting to feed propylene oxide.

(2) Pre-dripping propylene oxide before feeding, stopping feeding when the pressure in the reaction kettle reaches positive pressure, observing the reaction condition, indicating that the materials start to react when the temperature rises and the pressure drops, and then continuously feeding propylene oxide, wherein the temperature is controlled to be 90-100 ℃.

(3) And when the temperature reaches 100 ℃, continuously feeding propylene oxide, slowly feeding in the early stage, raising the temperature by using reaction heat, controlling the reaction temperature to be 90-155 ℃, and starting an external circulating pump after the feeding is finished. The temperature is raised by the reaction heat of the materials as much as possible, heating is not needed, local overheating is prevented, the color depth is avoided, and the pressure intensity does not exceed 0.60MPa in the reaction process of the materials.

(4) Maintaining the reaction temperature for curing until the pressure is not changed, wherein in the process, the curing temperature is controlled within the range of 90-135 ℃ in the first 2 hours, and the curing temperature is controlled within the range of 135-155 ℃ in the second 2 hours.

The halogen-containing reactive flame-retardant polyether polyol prepared by the method has the advantages of moderate viscosity, high reaction activity and the like, and the prepared polyurethane foam plastic has the characteristics of high strength, good dimensional stability, low heat conductivity coefficient, strong binding power, permanent flame retardance and the like, and is widely suitable for producing polyurethane foams such as high-flame-retardant spraying and plate materials.