阅读说明：本技术 一种溴硝醇反应型阻燃聚醚多元醇的制备方法 (Preparation method of bronopol reaction type flame-retardant polyether polyol ) 是由 翟洪金 胡其标 应珏 王挺 于 2020-12-15 设计创作，主要内容包括：本发明公开了一种溴硝醇反应型阻燃聚醚多元醇的制备方法,以溴硝醇为起始剂,在催化剂作用下,与环氧丙烷、环氧乙烷的一种或两种混合物进行开环聚合反应,聚合结束后,精制得阻燃聚醚多元醇成品。采用该阻燃聚醚制备的聚氨酯泡沫具有良好的阻燃效果,相对于外加阻燃剂制备的聚氨酯泡沫塑料阻燃性能稳定,泡沫质量更好。(The invention discloses a preparation method of bronopol reaction type flame-retardant polyether polyol, which takes bronopol as an initiator to carry out ring-opening polymerization reaction with one or two mixtures of propylene oxide and ethylene oxide under the action of a catalyst, and after the polymerization is finished, the flame-retardant polyether polyol finished product is obtained by refining. The polyurethane foam prepared from the flame-retardant polyether has a good flame-retardant effect, and has stable flame-retardant performance and better foam quality compared with polyurethane foam prepared from an additional flame retardant.)

1. A preparation method of bronopol reaction type flame retardant polyether polyol is characterized in that: taking bronopol as an initiator, adding a catalyst potassium hydroxide, melting, and then preserving heat for dehydration; then carrying out ring-opening polymerization reaction with one or two of propylene oxide and ethylene oxide to obtain crude ether, and finally refining to obtain the finished product of the flame-retardant polyether polyol, wherein the weight ratio of the bronopol to the one or two of the propylene oxide and the ethylene oxide is 1:5-25, and the usage amount of the catalyst is 0.1-0.6% of the total amount of the product.

2. The process for preparing a bronopol-reactive flame retardant polyether polyol as claimed in claim 1, wherein: the catalyst is one or a mixture of potassium hydroxide, sodium methoxide and potassium methoxide.

3. The process for preparing a bronopol-reactive flame retardant polyether polyol as claimed in claim 1, wherein: the melting temperature is 120-150 ℃.

4. The process for preparing a bronopol-reactive flame retardant polyether polyol as claimed in claim 1, wherein: the temperature of the heat preservation and dehydration is 120 plus materials, and the vacuum degree is less than or equal to minus 0.098 MPa.

5. The process for preparing a bronopol-reactive flame retardant polyether polyol as claimed in claim 1, wherein: the ring-opening polymerization temperature is 130-150 ℃, and the reaction pressure is-0.10-0.4 MPa.

6. The process for preparing a bronopol-reactive flame retardant polyether polyol according to any one of claims 1 to 5, wherein: after the ring-opening polymerization reaction is finished, adding water into the crude ether, stirring for 5-15min at the temperature of 50-65 ℃, adding phosphoric acid for neutralization for 10-20min, adding a polyether refined adsorbent at the temperature of 60-70 ℃ to complete adsorption, then heating to the temperature of 120 ℃ and 125 ℃, dehydrating for 1-2h under the condition that the vacuum degree is less than or equal to-0.098 MPa, cooling to the temperature below 70 ℃, discharging, and refining the obtained crude product to obtain a finished product; wherein, the usage amount of the deionized water is 2 to 10 percent of the total amount of the crude ether, the usage amount of the phosphoric acid is 0.2 to 1.2 percent of the total amount of the crude ether, and the usage amount of the polyether refined adsorbent is 0.2 to 1 percent of the total amount of the crude ether.

Technical Field

The invention belongs to the technical field of preparation or chemical processing of organic high molecular compounds, and relates to a preparation method of bronopol reaction type flame retardant polyether polyol,

background

Polyether polyol is one of main raw materials for synthesizing polyurethane materials, and along with the expansion of the application field of polyurethane and the improvement of national fire safety requirements, people have higher and higher requirements on the flame retardant property of the polyurethane. At present, polyurethane foam flame retardance mainly comprises two methods, namely an additive flame retardant method and a reaction flame retardant method. Wherein, the additive flame retardant is mainly a compound which does not have active reaction groups and contains flame retardant elements such as chlorine, bromine, phosphorus and the like; the reactive flame retardant is an additive with reactivity, which is prepared by introducing flame retardant elements such as chlorine, bromine, phosphorus and the like into polyether polyol or isocyanate molecules serving as main raw materials of a polyurethane material. Nowadays, the ideal flame retardant effect is difficult to achieve by the traditional additive flame retardant. Therefore, the reactive flame-retardant polyether polyol is increasingly gaining wide attention and acceptance in the market.

At present, the reactive flame-retardant polyether which can be applied to the field of polyurethane foam in the market has few types, the polyether preparation process is complex, the flame-retardant effect is not high, and the application of the polyether is limited to a certain extent, so that the reactive flame-retardant polyether with simple and convenient preparation process and high flame retardance is urgently needed in the market.

Disclosure of Invention

The invention aims to provide a preparation method of bronopol reaction type flame retardant polyether polyol, and polyurethane foam prepared from the flame retardant polyether has good flame retardant effect, and has stable flame retardant performance and better foam quality compared with polyurethane foam prepared from an additional flame retardant.

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

a process for preparing the flame-retarding polyether polyol by reaction of bromonitro alcohol includes ring-opening polymerizing reaction between bromonitro alcohol as initiator and one or two of epoxypropane and epoxyethane under the action of catalyst, and refining. Wherein, the weight ratio of the bronopol to one or two of the propylene oxide and the ethylene oxide is 1:5-25, and the usage amount of the catalyst is 0.1-0.6% of the total amount of the product.

The catalyst is one or a mixture of potassium hydroxide, sodium methoxide and potassium methoxide.

The invention relates to a preparation method of bronopol reaction type flame retardant polyether polyol, which comprises the following steps:

the first step is as follows: adding an initiator of bronopol and a catalyst, melting at the temperature of 120-150 ℃, and dehydrating for 1h in vacuum at the temperature of 150 ℃.

The second step is that: after dehydration, introducing one or two mixtures of propylene oxide and ethylene oxide, and carrying out ring-opening polymerization reaction under the action of a catalyst potassium hydroxide at the reaction temperature of 130-150 ℃ and the reaction pressure of-0.10-0.4 MPa.

The third step: after the polymerization reaction is finished, vacuumizing and degassing at 150 ℃ for 0.5 h. Crude ether was obtained.

The fourth step: and refining the obtained polyether polyol crude product. Adding deionized water for hydrolysis, adding phosphoric acid for neutralization, adding a polyether refining agent for adsorption, and then dehydrating and filtering to obtain the target flame-retardant polyether polyol. Wherein, the usage amount of the deionized water is 2 to 10 percent of the total amount of the crude ether, the usage amount of the phosphoric acid is 0.2 to 1.2 percent of the total amount of the crude ether, and the usage amount of the polyether refined adsorbent is 0.2 to 1 percent of the total amount of the crude ether.

The invention has the following beneficial effects:

(1) because the bronopol contains a nitrogen halogen structure:the prepared flame-retardant polyether polyol has a nitrogen-halogen synergistic flame-retardant effect and can achieve a higher flame-retardant effect.

(2) The bromine nitryl alcohol is used as a single initiator, and the flame-retardant polyether containing nitrogen halide flame-retardant effect can be synthesized without compounding.

(3) Provides a novel flame-retardant polyether polyol product for the flame-retardant polyether polyol market, and enriches the market selectivity of the flame-retardant polyether.

Detailed Description

A process for preparing the flame-retarding polyether polyol by reaction of bromonitro alcohol includes ring-opening polymerizing reaction between bromonitro alcohol as initiator and one or two of epoxypropane and epoxyethane under the action of catalyst, and refining. Wherein, the weight ratio of the bronopol to one or two of the propylene oxide and the ethylene oxide is 1:5-25, and the usage amount of the catalyst is 0.1-0.6% of the total amount of the product. The catalyst is one or a mixture of potassium hydroxide, sodium methoxide and potassium methoxide.

Example 1

(1) Adding 200g of bronopol into a reaction kettle, adding 3.0g of potassium hydroxide, replacing the air in the reaction kettle with nitrogen twice, heating to 120-150 ℃, melting, and carrying out vacuum dehydration for 1h at 150 ℃. Then 1300g of propylene oxide is dripped to react, the reaction temperature is controlled at 130-150 ℃, and the pressure is less than 0.4 MPa. After the reaction of the propylene oxide is finished, vacuumizing and degassing for 0.5h at 150 ℃. 1500g of crude ether were obtained.

(2) Adding 105g of deionized water into the obtained crude ether, stirring for 10 minutes at the temperature of 50 ℃, adding 6.5g of phosphoric acid for neutralization for 20 minutes, adding 6g of polyether refined adsorbent for adsorption for 10 minutes, wherein the adsorption temperature is 60-70 ℃, then heating to 125 ℃, keeping the temperature and dehydrating for 1.5 hours under the vacuum degree of less than or equal to-0.098 MPa, then cooling to 65 ℃, and filtering to obtain the required flame-retardant polyether polyol.

(3) The hydroxyl value of the refined flame-retardant polyether polyol is 74.8mgKOH/g, and the viscosity is 700 mPa.s/25 ℃. The prepared polyurethane foam has an oxygen index of 28.1.

Example 2

(1) Adding 100g of bronopol into a reaction kettle, adding 4.0g of potassium methoxide, replacing the air in the reaction kettle with nitrogen twice, heating to 120-150 ℃, melting, and carrying out vacuum dehydration for 1h at 150 ℃. Then 1200g of propylene oxide is dripped to react, the reaction temperature is controlled at 130-150 ℃, and the pressure is less than 0.4 MPa. After the reaction of the propylene oxide is finished, vacuumizing and degassing for 0.5h at 150 ℃. 1300g of crude ether was obtained.

(2) Adding 91g of deionized water into the obtained crude ether, stirring for 10 minutes at the temperature of 50 ℃, adding 6.2g of phosphoric acid for neutralization for 20 minutes, adding 5g of polyether refined adsorbent for adsorption for 10 minutes, wherein the adsorption temperature is 60-70 ℃, then heating to 125 ℃, keeping the temperature and dehydrating for 1.5 hours under the vacuum degree of less than or equal to-0.098 MPa, then cooling to 65 ℃, and filtering to obtain the required flame-retardant polyether polyol.

(3) The hydroxyl value of the refined flame-retardant polyether polyol is 43.1mgKOH/g, and the viscosity is 1100 mPa.s/25 ℃. The prepared polyurethane foam has an oxygen index of 29.3.

Example 3

(1) Adding 200g of bronopol into a reaction kettle, adding 2.0g of sodium methoxide, replacing the air in the reaction kettle with nitrogen twice, heating to 120-150 ℃, melting, and carrying out vacuum dehydration for 1h at 150 ℃. Then 1200g of ethylene oxide is dripped to react, the reaction temperature is controlled at 130-150 ℃, and the pressure is less than 0.4 MPa. After the reaction of ethylene oxide is finished, vacuum degassing is carried out for 0.5h at 150 ℃. 1400g of crude ether was obtained.

(2) Adding 98g of deionized water into the obtained crude ether, stirring for 10 minutes at the temperature of 50 ℃, adding 4.3g of phosphoric acid for neutralization for 20 minutes, adding 4g of polyether refined adsorbent for adsorption for 10 minutes, wherein the adsorption temperature is 60-70 ℃, then heating to 125 ℃, keeping the temperature and dehydrating for 1.5 hours under the vacuum degree of less than or equal to-0.098 MPa, then cooling to 65 ℃, and filtering to obtain the required flame-retardant polyether polyol.

(3) The hydroxyl value of the refined flame-retardant polyether polyol is 80.1mgKOH/g, and the viscosity is 560 mPa.s/25 ℃. The prepared polyurethane foam has an oxygen index of 27.5.

Example 4

(1) Adding 80g of bronopol, 3.0g of potassium hydroxide and 2.0g of potassium methoxide into a reaction kettle, replacing the air in the kettle with nitrogen twice, heating to 120 ℃ and 150 ℃ to melt the bronopol, and carrying out vacuum dehydration for 1h at 150 ℃. Then, a mixture of 1000g of propylene oxide and 320g of ethylene oxide is dropped into the mixture for reaction, the reaction temperature is controlled to be 130-150 ℃, and the pressure is less than 0.4 MPa. After the reaction is finished, vacuumizing and degassing at 150 ℃ for 0.5 h. 1400g of crude ether was obtained.

(2) Adding 98g of deionized water into the obtained crude ether, stirring for 10 minutes at the temperature of 50 ℃, adding 10.5g of phosphoric acid for neutralization for 20 minutes, adding 6g of polyether refined adsorbent for adsorption for 10 minutes, wherein the adsorption temperature is 60-70 ℃, then heating to 125 ℃, keeping the temperature and dehydrating for 1.5 hours under the vacuum degree of less than or equal to-0.098 MPa, then cooling to 65 ℃, and filtering to obtain the required flame-retardant polyether polyol.

(3) The hydroxyl value of the refined flame-retardant polyether polyol is 32.1mgKOH/g, and the viscosity is 1480mPa & s/25 ℃. The prepared polyurethane foam has an oxygen index of 28.7.

The above description is provided for the purpose of describing the preferred embodiments of the present invention in more detail, and it should not be construed that the embodiments of the present invention are limited to the description above, and it will be apparent to those skilled in the art that the present invention can be implemented in many different forms without departing from the spirit and scope of the present invention.