Flame-retardant polyether polyol for high-density spraying as well as preparation method and application of flame-retardant polyether polyol

Abstract

The invention discloses flame-retardant polyether polyol for high-density spraying as well as a preparation method and application of the flame-retardant polyether polyol, and belongs to the technical field of all-water spraying flame retardance. According to the technical scheme, the flame-retardant polyether polyol for high-density spraying is obtained by taking sucralose and small-molecular alcohol as composite initiators and reacting with epoxypropane under the action of an alkali metal catalyst, and the preparation method comprises the following steps of: preparing the flame-retardant polyether polyol for high-density spraying by taking the sucralose and the small-molecular alcohol as the composite initiators and taking the sucralose and the small-molecular alcohol as the composite initiators; comprising the following steps: 1) adding sucralose, small-molecular alcohol and water into a reaction kettle, adding an alkali metal catalyst, and sealing the reaction kettle; according to the flame-retardant polyether polyol for the high-density spraying, sucralose is introduced as an initiator and serves as a reactive flame retardant, and the defects that the flame-retardant effect is not lasting, compatibility is poor, the performance of a polyurethane material is prone to being reduced and the like generally existing in a common additive type flame retardant are overcome.

Description

Technical Field

[0001] The invention belongs to the technical field of full-water spray flame retardancy, and specifically relates to a flame retardant polyether polyol for high-density spraying, and a preparation method and application thereof. Background Art

[0002] In recent years, with the increasing attention paid to environmental protection and fire safety around the world, the flame retardant properties of polymer materials have become the focus of the industry. Polyurethane, as a polymer material with excellent performance, is widely used in various fields of life. However, the chemical composition of polyurethane foam is mainly composed of highly flammable elements such as oxygen, carbon, and hydrogen. The oxygen index of ordinary rigid polyurethane foam is usually 17-19%. At the same time, ordinary polyurethane foam produces highly toxic gases such as HCN and CO when burning, posing a huge threat to people's lives and property. Therefore, the flame retardant properties of polyurethane foam are of great significance to the polyurethane industry.

[0003] The main ways to improve the flame retardant properties of polyurethane materials are mainly divided into two categories according to different methods: additive type and reactive type. Additive flame retardants (such as TCPP, TCEP, DMMP, etc.) are flame retardants that can be directly added to plastics and do not react physically or chemically with reactants. They have the advantages of high flame retardancy and low price, and are widely used in industrial production. However, this type of flame retardant has the disadvantages of not lasting flame retardant effect, poor compatibility and easy reduction of polyurethane material performance, and is difficult to use in occasions with high flame retardant efficiency requirements. The reactive type mainly enters the main chain structure of polyurethane as an initiator, and can also introduce corresponding functional groups or side chains as needed to meet special performance requirements. It is the most popular type of flame retardant. However, compared with additive flame retardants, the types of reactive flame retardants are less and the application range is narrower, which to a certain extent limits the wide application of reactive flame retardants in polyurethane materials. Summary of the invention

[0004] The present invention provides a flame retardant polyether polyol for high-density spraying, a preparation method and application thereof, wherein sucralose is introduced as an initiator and added into the polyurethane main chain structure as a reactive flame retardant, thereby overcoming the common shortcomings of common additive flame retardants, such as short-lasting flame retardant effect, poor compatibility and easy reduction of polyurethane material performance.

[0005] The technical solution of the present invention is: In the first aspect, a flame retardant polyether polyol for high-density spraying is disclosed, wherein sucralose and small molecule alcohols are used as composite initiators, and react with propylene oxide under the action of an alkali metal catalyst to obtain a flame retardant polyether polyol for high-density spraying, wherein the functionality is 3.5-4.4 and the hydroxyl value is 280-400 mgKOH / g; wherein: The small molecule alcohol is one of glycerol, diethylene glycol or trimethylolpropane; The chemical name of the sucralose is 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose, and the molecular formula is C 12 H 19 O8Cl3, molecular weight is 397.64, its structure is as follows: .

[0006] In a second aspect, a method for preparing the flame-retardant polyether polyol for high-density spraying is disclosed, comprising the following steps: 1) Place sucralose, small molecule alcohols and water into a reactor, add an alkali metal catalyst, seal the reactor, evacuate to -0.09 MPa after nitrogen replacement, and heat to 80-90°C; 2) Add propylene oxide for the first time, control the actual temperature of the material at 80-90°C during the addition process, and mature for 2-3 hours after the addition is completed; raise the temperature to 90-130°C, add propylene oxide for the second time, control the temperature at 100-130°C during the addition process, until all the propylene oxide is added, and mature for 2-3 hours to obtain a crude polyether; 3) Removal of unreacted monomers; 4) Post-treatment: reduce the temperature in the reactor to 75-85°C, add phosphoric acid and water, stir for 1-2h, add adsorbent, raise the temperature to 100-110°C, vacuum dehydrate and control the pressure in the reactor at -0.08~-0.09MPa, time for 3-5h, detect the moisture content below 0.1%, discharge and filter, and obtain high-density flame-retardant polyether polyol for spraying.

[0007] Preferably, the alkali metal catalyst is solid KOH.

[0008] Preferably, the first dropwise addition of propylene oxide accounts for 10%-35% of the total mass of propylene oxide.

[0009] Preferably, in step 4) post-treatment, the amount of phosphoric acid added is 0.6-0.8% of the mass of the crude polyether obtained by the polymerization reaction, preferably 0.7%. It should be noted that the mass of the crude polyether refers to the total amount of all sucralose, small molecule alcohols, catalysts and propylene oxide. The amount of pure water added is 7-9% of the mass of the crude polyether obtained by the polymerization reaction, preferably 8%. The amount of adsorbent added is 0.15-0.25% of the mass of the crude polyether obtained by the polymerization reaction, preferably 0.2%.

[0010] The third aspect discloses the application of the high-density flame-retardant polyether polyol for spraying in the preparation of high-density flame-retardant spraying materials. The high-density flame-retardant spraying materials are composed of component A and component B in a mass ratio of 1:1, in parts by weight, wherein component A includes the following raw materials in parts by weight: 100 parts of the prepared high-density flame-retardant polyether polyol for spraying, 1.5 parts of deionized water, 1 part of PC-8 catalyst, 2 parts of rigid foam silicone oil, 25 parts of HFC-365mfc foaming agent, and component B is polyphenyl polymethylene polyisocyanate; the preparation method is: first mix component A, and then mix component A and component B in a mass ratio of 1:1 to prepare a high-density flame-retardant spraying material.

[0011] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention introduces sucralose as an initiator to prepare a polyether polyol, wherein the functionality is 3.5-4.4 and the hydroxyl value is 280-400 mgKOH / g. By controlling the functionality and hydroxyl value of the polyether polyol, the polyether polyol has suitable viscosity and strength, and is better suitable for spraying materials. The polyether polyol is used to prepare a high-density flame-retardant spray material, which has the high strength and good dimensional stability of the sucrose polyether material, and adds halogen to improve the oxygen index, which can reach 23%, thereby increasing the flame retardancy of the material.

[0012] 2. The present invention introduces sucralose as an initiator and adds it into the main chain structure of polyurethane as a reactive flame retardant, thereby overcoming the common shortcomings of common additive flame retardants, such as short-lasting flame retardant effect, poor compatibility and easy reduction of polyurethane material performance. DETAILED DESCRIPTION

[0013] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments.

[0014] Example 1 The preparation method of the flame-retardant polyether polyol for high-density spraying is as follows: 1) 400 g of sucralose, 106 g of diethylene glycol and 100 g of water were placed in a polymerization reactor, followed by 3 g of KOH solid. The reactor was sealed, and the atmosphere was evacuated to -0.09 MPa after nitrogen replacement for 3 times, and the temperature was raised to 85°C. 2) Add propylene oxide for the first time, control the temperature in the polymerization kettle at 82.5±2.5℃, continuously add 48g of propylene oxide, control the actual temperature of the material to react between 82.5±2.5℃, control the pressure in the polymerization kettle at a feed rate to be less than the maximum pressure of 0.4MPa that the reactor can withstand, and after the addition is complete, mature for 2h, heat to 100℃, and perform vacuum dehydration to control the moisture content of the material in the kettle to less than 0.1%. Control the temperature in the polymerization kettle at 110±2.5℃, the pressure less than 0.4MPa, and continuously add propylene oxide, add 428g of propylene oxide, complete the addition, mature for 3h, and obtain crude polyether; 3) Control the temperature in the polymerization kettle between 112.5±2.5℃, control the pressure in the polymerization kettle between -0.08 and -0.09MPa by vacuuming, and remove the unreacted propylene oxide monomer for 1h; 4) Lower the temperature in the reactor to 80±2.5℃, add 5.92g of phosphoric acid and 69.02g of water, stir for 1h, add 1.48g of magnesium silicate, raise the temperature to 105±2.5℃, vacuum dehydrate and control the pressure in the reactor between -0.08 and -0.09MPa, time for 4h, detect the moisture content below 0.1%, discharge and filter to obtain qualified polyether polyol products. The polyether polyol with a hydroxyl value of 397mgKOH / g and a viscosity of 3670mPa·s was obtained.

[0015] Example 2 The preparation method of the flame-retardant polyether polyol for high-density spraying is as follows: 1) 400 g of sucralose, 40 g of glycerol and 100 g of water were placed in a polymerization reactor, followed by 3.8 g of KOH solid. The reactor was sealed, and the atmosphere was replaced with nitrogen three times before being evacuated to -0.09 MPa. The temperature was raised to 80°C. 2) Control the temperature in the polymerization kettle at 82.5±2.5℃, continuously add 289g of propylene oxide, control the actual temperature of the material to react between 82.5±2.5℃, control the pressure in the polymerization kettle to be less than 0.4MPa at the feed rate, mature for 3h, raise the temperature to 90℃, perform vacuum dehydration operation to control the moisture content of the material in the polymerization kettle to be less than 0.1%. Control the temperature in the polymerization kettle at 102.5±2.5℃, the pressure is less than 0.4MPa, continuously add propylene oxide, add 536g of propylene oxide, complete the addition, mature for 3h, and obtain crude polyether; 3) Control the temperature in the polymerization kettle between 112.5±2.5°C, control the pressure in the polymerization kettle between -0.08 and -0.09 MPa by vacuuming, and remove the unreacted propylene oxide monomer for 1 hour.

[0016] 4) Lower the temperature in the reactor to 82.5±2.5℃, add 10.15g phosphoric acid and 114.21g water, stir for 1.5h, add 3.18g magnesium silicate, raise the temperature to 102.5±2.5℃, vacuum dehydrate to control the pressure in the polymerization reactor between -0.08 and -0.09MPa, time for 3h, detect the moisture content below 0.1%, discharge and filter to obtain qualified polyether polyol products. Polyether polyol with hydroxyl value of 284mgKOH / g and viscosity of 2433mPa·s was obtained.

[0017] Example 3 The preparation method of the flame-retardant polyether polyol for high-density spraying is as follows: 1) 300 g of sucralose, 100 g of trimethylolpropane and 75 g of water were added into a polymerization reactor, and then 3.1 g of KOH solid was added. The reactor was sealed, and the atmosphere was replaced with nitrogen three times, and then vacuumed to -0.09 MPa, and the temperature was raised to 90°C; 2) Control the temperature in the polymerization kettle at 87.5±2.5℃, continuously add 141g of propylene oxide, control the actual temperature of the material to react between 87.5±2.5℃, control the pressure in the kettle to be less than 0.4MPa at the feed rate, mature for 2.5h, raise the temperature to 130℃, perform vacuum dehydration operation to control the moisture content of the material in the kettle to be less than 0.1%. Control the temperature in the polymerization kettle at 127.5±2.5℃, the pressure is less than 0.4MPa, continuously add propylene oxide, add 474g of propylene oxide, complete the addition, mature for 2.5h, and obtain crude polyether; 3) Control the temperature in the autoclave between 112.5±2.5℃, evacuate the autoclave to control the pressure between -0.08 and -0.09MPa, and remove the unreacted propylene oxide monomer for 1 hour; 4) Lower the temperature in the reactor to 77.5±2.5℃, add 7.19g phosphoric acid and 82.24g water, stir for 2h, add 2.05g magnesium silicate, raise the temperature to 107.5±2.5℃, vacuum dehydrate to control the pressure in the reactor between -0.08 and -0.09MPa, time for 5h, detect the moisture content below 0.1%, discharge and filter to obtain qualified polyether polyol products. The polyether polyol with hydroxyl value of 341mgKOH / g and viscosity of 2856mPa·s was obtained.

[0018] Comparative Example 1 The preparation method of the polyether polyol is as follows: 1) 250 g of sucralose, 130 g of diethylene glycol, and 62.5 g of water were placed in a polymerization reactor, and then 2.5 g of KOH solid was added. The reactor was sealed, and the atmosphere was replaced with nitrogen three times, and then vacuumed to -0.09 MPa, and the temperature was raised to 85°C; 2) Add propylene oxide for the first time, control the temperature in the polymerization kettle at 82.5±2.5℃, continuously add 41g of propylene oxide, control the actual temperature of the material to react between 82.5±2.5℃, control the pressure in the polymerization kettle to be less than 0.4MPa at the feed rate, mature for 2h, raise the temperature to 100℃, perform vacuum dehydration operation to control the moisture content of the material in the kettle to less than 0.1%. Control the temperature in the polymerization kettle at 110±2.5℃, the pressure is less than 0.4MPa, continuously add propylene oxide, add 361g of propylene oxide, complete the addition, and mature for 3h; 3) Control the temperature in the polymerization kettle between 112.5±2.5℃, control the pressure in the polymerization kettle between -0.08 and -0.09MPa by vacuuming, and remove the unreacted propylene oxide monomer for 1h; 4) Lower the temperature in the reactor to 80±2.5℃, add 4.7g phosphoric acid and 54.88g water, stir for 1h, add 1.17g magnesium silicate, raise the temperature to 105±2.5℃, vacuum dehydrate and control the pressure in the reactor between -0.08 and -0.09MPa, time for 4h, detect the moisture content below 0.1%, discharge and filter to obtain qualified polyether polyol products. The polyether polyol with hydroxyl value of 402mgKOH / g and viscosity of 467mPa·s was obtained.

[0019] Comparative Example 2 The preparation method of the polyether polyol is as follows: 1) 400 g of sucralose, 5 g of diethylene glycol and 100 g of water were placed in a polymerization reactor, and then 2.5 g of KOH solid was added. The reactor was sealed, and the atmosphere was replaced with nitrogen three times, and then vacuumed to -0.09 MPa and heated to 85°C. 2) Add propylene oxide for the first time, control the temperature in the polymerization kettle at 82.5±2.5℃, continuously add 31g of propylene oxide, control the actual temperature of the material to react between 82.5±2.5℃, control the pressure in the polymerization kettle to be less than 0.4MPa at the feed rate, complete the addition, mature for 2h, obtain crude polyether, heat to 100℃, perform vacuum dehydration operation to control the moisture content of the material in the kettle to be less than 0.1%. Control the temperature in the polymerization kettle at 110±2.5℃, the pressure is less than 0.4MPa, continuously add propylene oxide, add 280g of propylene oxide, complete the addition, and mature for 3h; 3) Control the temperature in the polymerization kettle between 112.5±2.5℃, control the pressure in the polymerization kettle between -0.08 and -0.09MPa by vacuuming, and remove the unreacted propylene oxide monomer for 1h; 4) Lower the temperature in the reactor to 80±2.5℃, add 4.3g phosphoric acid and 50.26g water, stir for 1h, add 1.07g magnesium silicate, raise the temperature to 105±5℃, vacuum dehydrate and control the pressure in the reactor between -0.08 and -0.09MPa, time for 4h, detect the moisture content below 0.1%, discharge and filter to obtain qualified polyether polyol products. The polyether polyol with hydroxyl value of 404mgKOH / g and viscosity of 12089mPa·s is obtained, but it is not suitable for spraying system due to its high viscosity.

[0020] Comparative Example 3 The preparation method of the polyether polyol is as follows: 1) Put 400g of sucrose, 220g of diethylene glycol and 100g of water into a polymerization kettle, then add 6g of KOH solid, seal the kettle, replace with nitrogen 3 times, evacuate to -0.09MPa, and heat to 85℃; 2) Add propylene oxide for the first time, control the temperature in the polymerization kettle at 82.5±2.5℃, continuously add 127g of propylene oxide, control the actual temperature of the material to react between 82.5±2.5℃, control the pressure in the polymerization kettle to be less than 0.4MPa at the feed rate, complete the addition, mature for 2h, raise the temperature to 100℃, obtain crude polyether, and perform vacuum dehydration to control the moisture content of the material in the kettle to be less than 0.1%. Control the temperature in the polymerization kettle at 110±2.5℃ and the pressure to be less than 0.4MPa, continuously add propylene oxide, add 1141g of propylene oxide, complete the addition, and mature for 3h; 3) Control the temperature in the polymerization kettle between 112.5±2.5℃, control the pressure in the polymerization kettle between -0.08 and -0.09MPa by vacuuming, and remove the unreacted propylene oxide monomer for 1h; 4) Lower the temperature in the reactor to 80±2.5℃, add 11.36g phosphoric acid and 132.58g water, stir for 1h, add 2.84g magnesium silicate, raise the temperature to 105±2.5℃, vacuum dehydrate and control the pressure in the reactor between -0.08 and -0.09MPa, time for 4h, detect the moisture content below 0.1%, discharge and filter to obtain qualified polyether polyol products. The polyether polyol with hydroxyl value of 394mgKOH / g and viscosity of 3318mPa·s was obtained.

[0021] The high-density flame-retardant spray material is prepared by using the polyether polyol prepared in the embodiment and the comparative example. The high-density flame-retardant spray material is composed of component A and component B in a mass ratio of 1:1, and the specific weight ratio is: Component A: Weigh 100 parts of polyether polyol, 1.5 parts of deionized water, 1 part of PC-8 catalyst, 2 parts of hard foam silicone oil, and 25 parts of HFC-365mfc foaming agent; mix the weighed materials evenly to obtain component A. Component B is polyphenyl polymethylene polyisocyanate. Component A and component B are mixed at a mass ratio of 1:1 at 25°C to prepare a high-density flame-retardant spray material. The product quality indicators are tested, and the performance data of the high-density flame-retardant spray material prepared using the polyether polyol prepared in the embodiment and the comparative example are shown in Table 1.

[0022] Table 1 Performance data of high density flame retardant spray materials

[0023] The test standard for oxygen index test is GB8624-2012 Classification of combustion performance of building materials and products.

[0024] Note: OHV stands for hydroxyl value, the unit is mgKOH / g, VIS stands for viscosity, the unit is mPa·s.

[0025] From the data in the table above, it can be seen that the oxygen index of the foam made of the polyether prepared by the general initiator in Comparative Example 3 is about 19. After adding halogen-containing sucralose in Examples 1-3, the oxygen index is significantly improved, and the flame retardant effect is good. It can be seen from Comparative Example 1 that the oxygen index is 20 at a lower functionality, which is due to the low functionality, in which the content of sucralose is reduced, resulting in a low oxygen index, but still has a small amount of flame retardant effect.

Claims

1. Flame retardant polyether polyol for high-density spraying, characterized in that: Sucralose and small molecule alcohols are used as composite initiators, and react with propylene oxide under the action of an alkali metal catalyst to obtain a flame retardant polyether polyol for high-density spraying, which has a functionality of 3.5-4.4 and a hydroxyl value of 280-400 mgKOH / g; wherein: The small molecule alcohol is one of glycerol, diethylene glycol or trimethylolpropane.

2. The method for preparing a flame-retardant polyether polyol for high-density spraying according to claim 1, characterized in that: The following steps are involved: 1) Place sucralose, small molecule alcohols and water into a reactor, add an alkali metal catalyst, seal the reactor, evacuate to -0.09 MPa after nitrogen replacement, and heat to 80-90°C; 2) Add propylene oxide for the first time, control the actual temperature of the material at 80-90°C during the addition process, and mature for 2-3 hours after the addition is completed; raise the temperature to 90-130°C, add propylene oxide for the second time, control the temperature at 100-130°C during the addition process, until all the propylene oxide is added, and mature for 2-3 hours to obtain a crude polyether; 3) Removal of unreacted monomers; 4) Post-treatment: reduce the temperature in the reactor to 75-85°C, add phosphoric acid and water, stir for 1-2h, add adsorbent, raise the temperature to 100-110°C, vacuum dehydrate and control the pressure in the reactor at -0.08~-0.09MPa, time for 3-5h, detect the moisture content below 0.1%, discharge and filter, and obtain high-density flame-retardant polyether polyol for spraying.

3. The method for preparing a flame-retardant polyether polyol for high-density spraying as claimed in claim 2, characterized in that: The alkali metal catalyst is solid KOH.

4. The method for preparing a flame-retardant polyether polyol for high-density spraying as claimed in claim 2, characterized in that: The first drop of propylene oxide accounts for 10%-35% of the total mass of propylene oxide.

5. The method for preparing a flame-retardant polyether polyol for high-density spraying as claimed in claim 2, characterized in that: In step 4) post-treatment, the amount of phosphoric acid added is 0.6-0.8% of the mass of the crude polyether obtained by the polymerization reaction, the amount of water added is 7-9% of the mass of the crude polyether obtained by the polymerization reaction, and the amount of adsorbent added is 0.15-0.25% of the mass of the crude polyether obtained by the polymerization reaction.

6. The method for preparing a flame-retardant polyether polyol for high-density spraying as claimed in claim 2, characterized in that: The adsorbent is magnesium silicate.

7. Use of the flame-retardant polyether polyol for high-density spraying as claimed in claim 1 in the preparation of high-density flame-retardant spraying materials, characterized in that: The high-density flame-retardant spray material is composed of component A and component B in a mass ratio of 1:1, wherein component A includes the following raw materials in parts by weight: 100 parts of flame-retardant polyether polyol for high-density spraying prepared according to claim 1, 1.5 parts of deionized water, 1 part of PC-8 catalyst, 2 parts of rigid foam silicone oil, 25 parts of HFC-365mfc foaming agent, and component B is polyphenyl polymethylene polyisocyanate; the preparation method is: firstly mix component A, and then mix component A and component B in a mass ratio of 1:1 to prepare the high-density flame-retardant spray material.

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