Highly adhesive reactive flame-retardant polyether polyol and preparation method thereof

Abstract

The present invention belongs to the technical field of polyether polyol synthesis, and specifically relates to a highly adhesive reactive flame-retardant polyether polyol and a preparation method thereof. The polyether polyol is prepared by the following steps: a solvent, a triphenyl alcohol compound, an aminophosphoric acid compound, and an acid catalyst are added to a reactor respectively, and a condensation reaction is performed by continuous dehydration to generate a phosphate intermediate containing an amino group and a benzene ring; an alkali metal catalyst is added to the intermediate after cooling, and after vacuuming, the temperature is raised by stirring, and an alkylene oxide is introduced into the reactor to perform a polymerization reaction to obtain a highly adhesive reactive flame-retardant polyether polyol. The present invention introduces a phosphorus element with flame-retardant properties and a large number of benzene ring structures into the molecular structure of the polyether polyol, thereby improving the strength and flame-retardant properties of the product; a triphenylsilanol structure is introduced into the molecular structure of the polyether polyol, so that the polyether has a good ability to reduce surface tension, can improve the wetting properties, and make the product have better adhesion to the substrate.

Description

Technical Field

[0001] The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a highly adhesive reactive flame-retardant polyether polyol and a preparation method thereof. Background Art

[0002] Rigid polyurethane foam is a flammable organic polymer material with a porous structure and a large specific surface area. Therefore, the flame retardancy of polyurethane foam has always been the focus of attention. The use of additive flame retardants has problems such as flame retardant migration, poor durability and a significant impact on material properties. Therefore, embedding flame retardant elements into molecules for structural flame retardancy is a more effective way to prepare high-efficiency flame retardant materials. Halogen-based flame retardants have been gradually banned in recent years because they produce a large amount of toxic and harmful gases during combustion, which seriously damages the surrounding environment. Therefore, halogen-free flame retardants have gradually become a market development trend.

[0003] Patent CN104151517A discloses a highly flame-retardant polyurethane-modified polyisocyanurate rigid foam exterior wall insulation material, which discloses a structural flame-retardant polyether polyol, which is prepared by first reacting triphenyl phosphate, diethanolamine and aldehyde solution at a mass ratio of 10-20:10-20:5-10 at 0-10°C to synthesize an initiator containing a nitrogen-phosphorus structure, and then reacting the initiator with oxirane at a mass ratio of 10-20:1-5 at room temperature, but the finished product has poor bonding properties.

[0004] In sandwich panels, refrigerators and other application areas, polyurethane foam can be directly bonded to the board and refrigerator shell during the foaming process. The bonding strength between it and the substrate directly affects whether the product can be used normally. If the bonding performance is poor, problems such as shelling will occur, which will have a great impact on the product. Therefore, better bonding performance means better application stability of polyurethane foam. Summary of the invention

[0005] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a highly adhesive reactive flame-retardant polyether polyol, which introduces phosphorus elements and benzene ring structures into the molecular structure of the polyether polyol through molecular structure design, and is applied to the field of polyurethane rigid foam, greatly improving the strength and flame retardant properties of the product, while having a bulk flame retardant effect. In addition, the triphenylsilanol structure in the present invention has a good ability to reduce surface tension, can improve the wetting properties of the polyether, and make the product have better adhesion to the substrate.

[0006] The invention also provides a preparation method thereof, which is simple and feasible and suitable for large-scale production.

[0007] The highly adhesive reactive flame-retardant polyether polyol of the present invention is prepared from the following raw materials in parts by weight:

[0008] 25-47 parts of a triphenyl alcohol compound;

[0009] 0.3-2.2 parts of alkali metal catalyst;

[0010] Acidic catalyst 0.006-1.73 parts;

[0011] 7-13 parts of aminophosphoric acid compound;

[0012] 40-64 parts of alkylene oxide.

[0013] The triphenyl alcohol compound is triphenylsilanol.

[0014] The aminophosphoric acid compound is one or both of (1-aminobutyl)phosphoric acid and 4-aminobutylphosphoric acid.

[0015] The alkylene oxide is one or more of ethylene oxide, propylene oxide and butylene oxide.

[0016] The alkali metal catalyst is one or both of sodium hydroxide and potassium hydroxide.

[0017] The method for preparing the highly adhesive reactive flame-retardant polyether polyol is prepared by the following steps:

[0018] (1) adding a solvent, a triphenyl alcohol compound, an aminophosphoric acid compound, and an acidic catalyst into a reaction kettle respectively, evacuating the reactor, stirring and heating the reactor, and continuously dehydrating the reactor to perform a condensation reaction to generate a phosphate intermediate containing an amino group and a benzene ring;

[0019] (2) After cooling, an alkali metal catalyst is added to the intermediate, the pH is adjusted to 10-13, and after evacuation, the temperature is raised with stirring, and alkylene oxide is introduced into the reaction kettle to carry out a polymerization reaction. The unreacted alkylene oxide and solvent are removed by heating and evacuation to obtain a highly adhesive reactive flame-retardant polyether polyol.

[0020] The acidic catalyst in step (1) is sulfuric acid, the mass of which accounts for 0.01-5% of the total mass of all materials in step (1), and the sulfuric acid is dilute sulfuric acid with a mass concentration of 38%.

[0021] The solvent in step (1) is dodecane, and the mass ratio of dodecane to triphenyl alcohol compound is (2-5):1.

[0022] The reaction pressure of the condensation reaction in step (1) is -0.1 to -0.09 MPa, the reaction time is 1 to 5 hours, and the reaction temperature is 150 to 180°C.

[0023] The reaction pressure of the polymerization reaction in step (2) is -0.09~0.35MPa, the reaction time is: 0.5~5h, and the reaction temperature is: 80~120℃.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1) The present invention introduces phosphorus elements with flame retardant properties and a large number of benzene ring structures into the molecular structure of polyether polyols through molecular structure design, which greatly improves the strength and flame retardant properties of the products.

[0026] 2) The functional groups with flame retardant effect in the present invention exist in the product polyether polyol in the form of chemical bonds. Compared with additive flame retardants, the flame retardant performance of the product is long-lasting and not easy to decay and precipitate, and has a bulk flame retardant effect.

[0027] 3) The present invention introduces a triphenylsilanol structure into the molecular structure of the polyether polyol through molecular structure design, so that the polyether has a good ability to reduce surface tension, can greatly improve the wetting performance, and make the product have better adhesion to the substrate. DETAILED DESCRIPTION

[0028] The present invention will be further described below with reference to the embodiments.

[0029] Unless otherwise specified, all raw materials used in the examples are commercially available.

[0030] Example 1

[0031] The method for preparing the highly adhesive reactive flame-retardant polyether polyol is prepared by the following steps:

[0032] (1) 100 g of dodecane was added to a reaction kettle, and 50 g of triphenylsilanol was added while stirring and heating. After stirring at 60° C. for 30 min, 13.9 g of (1-aminobutyl)phosphoric acid was added. Finally, 0.0065 g of 38% dilute sulfuric acid was added to the reaction kettle. The temperature was raised to 150° C. and the pressure was -0.09 MPa while vacuuming. Under this condition, continuous dehydration was carried out for condensation reaction for 5 h to generate a phosphate intermediate containing an amino group and a benzene ring.

[0033] (2) After the reaction, the temperature was lowered to 80°C, 0.33 g of potassium hydroxide was added to the reactor, and the reactor was evacuated to -0.09 MPa after pressure testing and nitrogen replacement. At 80°C, 43 g of propylene oxide was introduced, and the pressure was maintained at 0.35 MPa during the reaction. The reaction was continued at this temperature and pressure for 5 hours. After the reaction, the temperature was raised to 220°C, the pressure was evacuated to -0.08 MPa, and nitrogen bubbling was maintained for 30 minutes. The temperature was lowered to 90°C and the material was discharged to obtain a highly adhesive reactive flame-retardant polyether polyol. The basic indicators and performance indicators are shown in Tables 1 and 3.

[0034] Example 2

[0035] The method for preparing the highly adhesive reactive flame-retardant polyether polyol is prepared by the following steps:

[0036] (1) Add 300 g of dodecane to a reactor, add 60 g of triphenylsilanol while stirring, add 18 g of 4-aminobutylphosphoric acid after stirring at 60°C for 30 min, and finally add 4.1 g of 38% dilute sulfuric acid to the reactor, and heat the reactor to 180°C while evacuating the vacuum, and the pressure is -0.1 MPa. Under this condition, continuous dehydration is carried out for 1 hour to generate a phosphate intermediate containing an amino group and a benzene ring;

[0037] (2) After the reaction, the temperature was lowered to 120°C, 5.2 g of sodium hydroxide was added to the reactor, and the reactor was evacuated to -0.09 MPa after pressure testing and nitrogen replacement. At 120°C, 151 g of ethylene oxide was introduced, and the pressure was maintained at 0.35 MPa during the reaction. The reaction was continued at this temperature and pressure for 0.5 h. After the reaction, the temperature was raised to 220°C, the reactor was evacuated to -0.08 MPa, and nitrogen bubbling was maintained for 30 min. The temperature was lowered to 90°C and the material was discharged to obtain a highly adhesive reactive flame-retardant polyether polyol. The basic indicators and performance indicators are shown in Tables 1 and 3.

[0038] Example 3

[0039] The method for preparing the highly adhesive reactive flame-retardant polyether polyol is prepared by the following steps:

[0040] (1) 200 g of dodecane was added to a reaction kettle, and 50 g of triphenylsilanol was added while stirring and heating. After stirring at 60° C. for 30 min, 16 g of (1-aminobutyl)phosphoric acid was added. Finally, 2 g of 38% dilute sulfuric acid was added to the reaction kettle. The temperature was raised to 170° C. and the pressure was -0.09 MPa while vacuuming. Under this condition, continuous dehydration was carried out for 3 h to generate a phosphate intermediate containing an amino group and a benzene ring.

[0041] (2) After the reaction, the temperature was lowered to 100°C, 2.7 g of potassium hydroxide was added to the reactor, and the reactor was evacuated to -0.09 MPa after pressure testing and nitrogen replacement. At 110°C, 80 g of butylene oxide was introduced, and the pressure was maintained at 0.35 MPa during the reaction. The reaction was continued at this temperature and pressure for 2 h. After the reaction, the temperature was raised to 220°C, the reactor was evacuated to -0.08 MPa, and nitrogen bubbling was maintained for 30 min. The temperature was lowered to 90°C and the material was discharged to obtain a highly adhesive reactive flame-retardant polyether polyol. The basic indicators and performance indicators are shown in Tables 1 and 3.

[0042] Highly adhesive reactive flame retardant polyether polyol product indicators:

[0043] The test standards and methods used for polyether polyols are:

[0044] Hydroxyl value: Tested in accordance with GB / T 12008.3-1989 "Determination of hydroxyl value in polyether polyols";

[0045] Viscosity: Tested in accordance with GB / T 12008.7-2010 "Plastic polyether polyols Part 7: Determination of viscosity".

[0046] Table 1 Basic indicators of high-adhesive reactive flame-retardant polyether polyol products

[0047]

[0048] The polyether polyols synthesized in the examples and comparative examples were formulated according to the formula shown in Table 2 below to obtain a composite polyether polyol, wherein:

[0049] INOVOL R4110 is a conventional polyether polyol produced by Shandong INOVOL New Materials Co., Ltd.

[0050] H2O is a chemical foaming agent;

[0051] N,N-dimethylcyclohexylamine as catalyst;

[0052] TMR-2 is the catalyst, produced by Xindian Chemical Materials (Shanghai) Co., Ltd.;

[0053] BDMA (N,N-dimethylbenzylamine) is the catalyst;

[0054] Cyclopentane is a physical foaming agent;

[0055] TEGOSTAB B8460 is a silicone oil produced by Evonik Specialty Chemicals (Shanghai) Co., Ltd.

[0056] Table 2 Rigid polyurethane foam sample formula

[0057]

[0058] The above-mentioned combined polyether was mixed with isocyanate PM200 (Wanhua Chemical Group Co., Ltd.) to prepare a rigid polyurethane foam sample as follows:

[0059] Under the conditions of ambient temperature of 25°C and mold temperature of 45°C, the materials were accurately weighed according to the formula in Table 2, and prepared into a combined polyether in a 500mL beaker. 50 parts by weight of the combined polyether and 60 parts by weight of isocyanate PM200 were taken and fully stirred. When the system was uniform, stirring was stopped, and the stirred materials were poured into a constant temperature foaming molding mold. After the foam was foamed, matured and cured, it was taken out of the mold to obtain a polyurethane rigid foam sample.

[0060] The polyurethane rigid foam samples were tested for compressive strength performance according to standard GB / T 8813-2008.

[0061] The polyurethane rigid foam samples were tested for bonding properties according to standard GB / T 10007-2008.

[0062] The polyurethane rigid foam samples were tested for flame retardancy according to standard GB / T 2406.2-2009.

[0063] The indicators and properties of the polyurethane rigid foam samples prepared from the polyether polyols obtained in Examples 1-3 and Comparative Examples 1-2 are shown in Table 3:

[0064] Table 3 Performance indicators of highly adhesive reactive flame retardant polyether polyols

[0065]

[0066] As can be seen from Table 2, the shelling shear force of the products obtained by foaming all conventional polyether polyols in Examples 1-3 using the high-adhesive flame-retardant polyol obtained by the present invention to partially replace conventional polyols is significantly higher than that in Comparative Examples 1-2, and the adhesiveness is greatly improved. The strength and oxygen index of the products obtained by foaming all conventional polyether polyols in Comparative Example 2 are significantly improved. Compared with Comparative Example 1, the additive TCPP flame retardant method has significantly improved both the oxygen index and the flame retardant durability. Compared with the additive flame retardant, the flame retardant performance of the product is durable and not easy to decay and precipitate, and has a bulk flame retardant effect.

Claims

1. A highly adhesive reactive flame retardant polyether polyol, characterized in that: It is prepared from the following raw materials in parts by weight: 25-47 parts of a triphenyl alcohol compound; 0.3-2.2 parts of alkali metal catalyst; Acidic catalyst 0.006-1.73 parts; 7-13 parts of aminophosphoric acid compound; 40-64 parts of alkylene oxide; The triphenyl alcohol compound is triphenylsilanol; The aminophosphoric acid compound is one or both of (1-aminobutyl)phosphoric acid and 4-aminobutylphosphoric acid; The method for preparing the highly adhesive reactive flame-retardant polyether polyol is prepared by the following steps: (1) adding a solvent, a triphenyl alcohol compound, an aminophosphoric acid compound, and an acidic catalyst into a reaction kettle respectively, evacuating the reactor, stirring and heating the reactor, and continuously dehydrating the reactor to perform a condensation reaction to generate a phosphate intermediate containing an amino group and a benzene ring; (2) After cooling, an alkali metal catalyst is added to the intermediate, and after evacuation, the temperature is raised with stirring, and alkylene oxide is introduced into the reaction kettle to carry out a polymerization reaction. The unreacted alkylene oxide and solvent are removed by increasing the temperature and evacuation to obtain a highly adhesive reactive flame-retardant polyether polyol.

2. The highly adhesive reactive flame-retardant polyether polyol according to claim 1, characterized in that: The alkylene oxide is one or more of ethylene oxide, propylene oxide and butylene oxide.

3. The highly adhesive reactive flame-retardant polyether polyol according to claim 1, characterized in that: The alkali metal catalyst is one or both of sodium hydroxide and potassium hydroxide.

4. A method for preparing the highly adhesive reactive flame-retardant polyether polyol according to any one of claims 1 to 3, characterized in that: Prepared by the following steps: (1) adding a solvent, a triphenyl alcohol compound, an aminophosphoric acid compound, and an acidic catalyst into a reaction kettle respectively, evacuating the reactor, stirring and heating the reactor, and continuously dehydrating the reactor to perform a condensation reaction to generate a phosphate intermediate containing an amino group and a benzene ring; (2) After cooling, an alkali metal catalyst is added to the intermediate, and after evacuation, the temperature is raised with stirring, and alkylene oxide is introduced into the reaction kettle to carry out a polymerization reaction. The unreacted alkylene oxide and solvent are removed by increasing the temperature and evacuation to obtain a highly adhesive reactive flame-retardant polyether polyol.

5. The method for preparing the highly adhesive reactive flame-retardant polyether polyol according to claim 4, characterized in that: The acidic catalyst in step (1) is sulfuric acid.

6. The method for preparing a highly adhesive reactive flame-retardant polyether polyol according to claim 4, characterized in that: The solvent in step (1) is dodecane, and the mass ratio of dodecane to triphenyl alcohol compound is (2-5):

1.

7. The method for preparing a highly adhesive reactive flame-retardant polyether polyol according to claim 4, characterized in that: The reaction pressure of the condensation reaction in step (1) is -0.1 to -0.09 MPa, the reaction time is 1 to 5 hours, and the reaction temperature is 150 to 180°C.

8. The method for preparing a highly adhesive reactive flame-retardant polyether polyol according to claim 4, characterized in that: The reaction pressure of the polymerization reaction in step (2) is -0.09~0.35MPa, the reaction time is: 0.5~5h, and the reaction temperature is: 80~120℃.

Images