Polyether polyol composition for polyurethane foaming and preparation method thereof

Abstract

The invention discloses a polyether polyol composition for polyurethane foaming and a preparation method thereof, and relates to the technical field of polyurethane foaming materials. The polyether polyol composition for polyurethane foaming, prepared by the invention, is prepared by reacting a hydrogen-containing compound and a hydroxyl vinyl ether epoxy copolymer; the hydrogen-containing compound is prepared from hydroxyl phthalimide and grease-based polyester polyol; the heat resistance and the mechanical strength of the foamed polyurethane are improved; the hydroxyl vinyl ether epoxy copolymer is prepared by copolymerizing a hydroxyl vinyl ether copolymer and dialkyl maleate, carrying out ring-opening addition on the copolymerized product and epoxy chloropropane, and carrying out ring-closing reaction, so that the hardness and elasticity of the polyurethane foam are enhanced, and the stability of the foamed polyurethane is further improved.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane foam materials, in particular to a polyether polyol composition for polyurethane foaming and a preparation method thereof. Background Art

[0002] Polyurethane foam is a polymer porous material produced by the reaction of isocyanate and polyol. It has the characteristics of light weight, heat insulation, waterproof and elasticity, and is widely used in construction, automobiles, furniture and other fields. Its core advantage lies in its excellent thermal insulation performance, which is superior to traditional thermal insulation materials, and its closed-cell structure (closed-cell rate of more than 95%) gives it excellent waterproofness and adhesion, and it can firmly bond to various substrates such as metal and glass. According to the structure, it can be divided into soft foam and hard foam, which is quickly formed by high-pressure spraying or pouring process, and forms a seamless whole after curing, with a service life of up to 30 years. In recent years, the promotion of environmentally friendly foaming agents (such as fluorine-free formulas) has further enhanced its sustainability, making it a core material for energy-saving buildings such as passive houses.

[0003] The core raw materials for the preparation of currently used foamed polyurethanes are isocyanic acid and polyols, which form the main chain structure of the polyurethane through chemical reactions. Polyether polyols are easy to mix with other components and have good fluidity. However, the heat resistance and mechanical properties of the prepared foamed polyurethane still have room for improvement. Therefore, the present invention studies and prepares a polyether polyol composition for polyurethane foaming. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a polyether polyol composition for polyurethane foaming and a preparation method thereof.

[0005] The present invention proposes a technical solution to solve the above technical problems: a polyether polyol composition for polyurethane foaming, comprising a hydrogen-containing compound and a hydroxy vinyl ether epoxy copolymer; the hydrogen-containing compound comprises hydroxyphthalimide and an oil-based polyester polyol.

[0006] Preferably, the tetrahydrophthalic anhydride is prepared by reacting with a benzylalkanolamine derivative; the benzylalkanolamine derivative is prepared by reacting diaminodiphenylmethane with diethanolamine.

[0007] Preferably, the oil-based polyester polyol is prepared by reacting hydroxylated oleic acid, maleic anhydride and glycerol.

[0008] Preferably, the hydroxy vinyl ether epoxy copolymer is prepared by copolymerizing hydroxy vinyl ether with dialkyl maleate, followed by ring-opening addition reaction with epichlorohydrin and then ring-closing reaction.

[0009] Preferably, the method for preparing the polyether polyol composition for polyurethane foaming comprises the following specific steps:

[0010] S1. Under a nitrogen atmosphere, tetrahydrophthalic anhydride and a benzyl alcohol amine derivative were mixed in a mass ratio of 2:3-5, heated to 82-85°C, stirred evenly, and then a 12-16% potassium hydroxide solution (0.03-0.06 times the mass of tetrahydrophthalic anhydride) was added dropwise at a rate of 1-3 ml / min. The mixture was heated to 110-120°C and reacted for 6-8 hours. The pH was adjusted to 6.5-7.0 with 85% phosphoric acid, vacuum dehydration was performed, and filtration was performed to obtain hydroxyphthalimide.

[0011] S2. Mix hydroxylated oleic acid and maleic anhydride in a mass ratio of 100:1-3, heat to 140-150°C, react for 2-3 hours, add glycerol (0.2-0.3 times the mass of the hydroxylated oleic acid) and zinc oxide (0.004-0.006 times the mass of the hydroxylated oleic acid) as a catalyst, heat to 200-220°C, react for 1-2 hours, reduce pressure to 3-5 kPa, continue to react for 2-3 hours, cool to room temperature, dilute with methanol (an equal mass of the hydroxylated oleic acid), centrifuge, and rotary evaporate to obtain a grease-based polyester polyol.

[0012] S3. The hydroxyphthalimide and oil-based polyester polyol were mixed and stirred to obtain a hydrogen-containing compound;

[0013] S4. The hydroxy vinyl ether copolymer, epichlorohydrin, toluene and catalyst tetrabutylammonium bromide were mixed in a mass ratio of 1:2-3:5:0.01-0.03, heated to 80-100 ° C, reacted for 3-4 hours, and then a 14-16% sodium hydroxide solution of 1.1-1.2 times the mass of the hydroxy vinyl ether copolymer was added dropwise at a rate of 1-3 ml / min. The mixture was cooled to 30-60 ° C and the reaction was continued for 2-3 hours. The mixture was centrifuged and washed 1-3 times with a mass fraction of 20-30% dilute sulfuric acid, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain a hydroxy vinyl ether epoxy copolymer;

[0014] S5. Under a nitrogen atmosphere, the hydrogen-containing compound and potassium hydroxide were mixed in a mass ratio of 20:1-1.2, the temperature was raised to 60-70°C, 4.2-4.4 times the mass of the hydrogen-containing compound of the hydroxy vinyl ether epoxy copolymer was added, the temperature was raised to 100-102°C, the pressure was 0.2-0.4 MPa, the reaction was carried out for 1-2 hours, and then 10-15 times the mass of the hydrogen-containing compound of the hydroxy vinyl ether epoxy copolymer was added, the temperature was raised to 112-115°C, the reaction was continued for 3-4 hours, and then 0. The method comprises the following steps of: adding 11 to 0.12 times the mass of potassium hydroxide, cooling to 104 to 107° C., dehydrating for 1 to 2 hours, adding 8 to 10 times the mass of the hydrogen-containing compound in terms of hydroxy vinyl ether epoxy copolymer and 2.1 to 2.3 times the mass of the hydrogen-containing compound in terms of ethylene oxide, heating to 114 to 117° C., and keeping the pressure at 0.2 to 0.4 MPa, continuing the reaction for 1 to 2 hours, vacuum degassing, and adjusting the pH to 4.5 to 5.5 with a phosphoric acid solution with a mass fraction of 14 to 17%, to obtain a polyether polyol composition for polyurethane foaming.

[0015] Preferably, in the above step S1, the preparation method of the benzyl alcohol amine derivative is as follows: under a nitrogen atmosphere, diaminodiphenylmethane and diethanolamine are mixed and reacted uniformly, and then a potassium hydroxide solution with a mass fraction of 12 to 16% is added dropwise at a rate of 1 to 3 ml / min, and the mass ratio of diaminodiphenylmethane, diethanolamine and potassium hydroxide is 18 to 20:21:2. The temperature is raised to 90 to 92 ° C, and the reaction is carried out for 6 to 8 hours. The pH is adjusted to 6.5 to 7.0 with 85% phosphoric acid by mass, and the temperature is raised to 100 ° C for vacuum dehydration. The mixture is filtered while hot to obtain the benzyl alcohol amine derivative.

[0016] Preferably, in the above step S2, the preparation method of hydroxylated oleic acid is: oleic acid, acetic acid and concentrated sulfuric acid are mixed in a mass ratio of 100-120:5:1, heated to 40-50°C, reacted for 1-2 hours, and then 0.25-0.35 times the mass of oleic acid and 30% hydrogen peroxide are added dropwise at a rate of 1-3 ml / min. The reaction temperature is controlled at 50-60°C, and the reaction is continued for 5-6 hours. After hydrolysis with deionized water, the liquid is separated, and then the pH is neutralized to 6-7 with sodium carbonate, and vacuum rotary evaporation is performed to obtain hydroxylated oleic acid.

[0017] Preferably, in the above step S3, the mass ratio of hydroxyphthalimide to oil-based polyester polyol is 2:2-5.

[0018] Preferably, in the above step S4, the preparation method of the hydroxy vinyl ether copolymer is: under a nitrogen atmosphere, hydroxy vinyl ether, dialkyl maleate, ethanol and azobisisobutyronitrile are mixed in a mass ratio of 10:13-15:30:0.02-0.03, heated to 68-72°C, reacted for 5-7h, cooled, precipitated with methanol, filtered, and vacuum dried to obtain a hydroxy vinyl ether copolymer.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The polyether polyol composition for polyurethane foaming prepared by the present invention is prepared by reacting a hydrogen-containing compound with a hydroxy vinyl ether epoxy copolymer;

[0021] Hydrogen-containing compounds include hydroxyphthalimide and oil-based polyester polyols; hydroxyphthalimide is produced by the reaction of tetrahydrophthalic anhydride and benzylalkanolamine derivatives, which are produced by the reaction of diaminodiphenylmethane and diethanolamine; and oil-based polyester polyols are produced by the reaction of hydroxylated oleic acid, maleic anhydride, and glycerol. Hydroxyphthalimide and oil-based polyester polyols have good compatibility and form a cross-linked structure by strengthening the hydrogen bonding between molecules, thereby improving the heat resistance and mechanical strength of the foamed polyurethane.

[0022] The hydroxy vinyl ether epoxy copolymer is prepared by copolymerizing a hydroxy vinyl ether copolymer with a dialkyl maleate, followed by a ring-opening addition reaction with epichlorohydrin and then a ring-closing reaction. The polyether polyol composition made of the hydroxy vinyl ether epoxy copolymer and a hydrogen-containing compound can form a multiple rigid cross-linking structure of epoxy groups, hydroxyl groups and vinyl groups with isocyanate, which not only enhances the hardness and elasticity of the polyurethane foam, but also inhibits the hydrolysis of the polyurethane foam in a hot and humid environment, further improving the stability of the foamed polyurethane. DETAILED DESCRIPTION

[0023] The present invention is described in detail below through examples. It should be noted that the following examples are intended only to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Those skilled in the art may make non-essential improvements and adjustments to the present invention based on the above disclosure. Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art.

[0024] The polyether polyol compositions for polyurethane foaming prepared in the examples of the present invention and the comparative examples were used to prepare polyurethane foam: the polyether polyol composition for polyurethane foaming, deionized water, silicone oil stabilizer DABCO DC-5188, and catalyst triethylenediamine were mixed and stirred evenly, and then isocyanate was added. The mixture was stirred at 1000-2000 rpm for 3-6 seconds, foamed for 2-3 minutes, and cured in an oven at 70°C for 1 hour to prepare a soft polyurethane foam; the mass ratio of the polyether polyol composition for polyurethane foaming, deionized water, silicone oil stabilizer DABCO DC-5188, catalyst triethylenediamine, and isocyanate was 35:2:4:2:35.

[0025] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index test methods of the polyurethane foam prepared using the polyether polyol composition for polyurethane foaming prepared in the examples and comparative examples as follows:

[0026] Mechanical strength: The polyurethane foam was subjected to a tensile strength test according to GB / T 6344.

[0027] Rebound rate: The polyurethane foam was tested for rebound rate according to GB / T 6670.

[0028] Heat resistance: The polyurethane foam was aged at 140°C for 48 hours and the dimensional stability test was performed according to GB / T8811.

[0029] Heat and moisture resistance: The polyurethane foam was treated at 70°C and 95% relative humidity for 48 hours, and the dimensional stability test was carried out in accordance with GB / T8811.

[0030] Example 1

[0031] The preparation method of the polyether polyol composition for polyurethane foaming in this embodiment is as follows:

[0032] S1. Under a nitrogen atmosphere, diaminodiphenylmethane and diethanolamine were mixed and reacted uniformly, and then a 12% potassium hydroxide solution was added dropwise at a rate of 1 ml / min, the mass ratio of diaminodiphenylmethane, diethanolamine and potassium hydroxide was 18:21:2, the temperature was raised to 90 ° C, the reaction was continued for 6 h, the pH was adjusted to 6.5 with 85% phosphoric acid, the temperature was raised to 100 ° C, vacuum dehydration was performed, and hot filtration was performed to obtain a benzyl alcohol amine derivative; under a nitrogen atmosphere, tetrahydrophthalic anhydride and a benzyl alcohol amine derivative were mixed in a mass ratio of 2:3, the temperature was raised to 82 ° C, and the mixture was stirred uniformly. A 12% potassium hydroxide solution with a mass fraction of 0.03 times the mass of tetrahydrophthalic anhydride was added dropwise at a rate of 1 ml / min, the temperature was raised to 110 ° C, the reaction was continued for 6 h, the pH was adjusted to 6.5 with 85% phosphoric acid, vacuum dehydration was performed and filtration was performed to obtain hydroxyphthalimide;

[0033] S2. Oleic acid, acetic acid, and concentrated sulfuric acid were mixed in a mass ratio of 100:5:1, heated to 40°C, reacted for 1 hour, and then 30% hydrogen peroxide (0.25 times the mass of the oleic acid) was added dropwise at a rate of 1 ml / min. The reaction temperature was controlled at 50°C and the reaction was continued for 5 hours. The mixture was hydrolyzed with deionized water and separated. The pH was then neutralized with sodium carbonate to 6, and the mixture was evaporated under reduced pressure to obtain hydroxylated oleic acid. Hydroxylated oleic acid and maleic anhydride were mixed in a mass ratio of 100:1, heated to 140°C, reacted for 2 hours, glycerol (0.2 times the mass of the hydroxylated oleic acid) and zinc oxide (0.004 times the mass of the hydroxylated oleic acid) as a catalyst were added, heated to 200°C, reacted for 1 hour, and then reduced to 3 kPa. The reaction was continued for 2 hours, cooled to room temperature, and diluted with methanol (equal to the mass of the hydroxylated oleic acid). The mixture was centrifuged and evaporated to obtain an oil-based polyester polyol.

[0034] S3. The hydroxyphthalimide and the oil-based polyester polyol were mixed in a mass ratio of 2:2 to 5 and stirred to obtain a hydrogen-containing compound;

[0035] S4. Under a nitrogen atmosphere, hydroxy vinyl ether, dialkyl maleate, ethanol and azobisisobutyronitrile were mixed in a mass ratio of 10:13:30:0.02, heated to 68 ° C, reacted for 5 hours, cooled, precipitated with methanol, filtered, and dried in vacuo to obtain a hydroxy vinyl ether copolymer; a hydroxy vinyl ether copolymer, epichlorohydrin, toluene and catalyst tetrabutylammonium bromide were mixed in a mass ratio of 1:2:5:0.01, heated to 80 ° C, reacted for 3 hours, and then a 14% sodium hydroxide solution with a mass fraction of 1.1 times the mass of the hydroxy vinyl ether copolymer was added dropwise at a rate of 1 ml / min, cooled to 30 ° C, and continued to react for 2 hours. The mixture was centrifuged and washed once with a mass fraction of 20% dilute sulfuric acid, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain a hydroxy vinyl ether epoxy copolymer;

[0036] S5. Under a nitrogen atmosphere, the hydrogen-containing compound and potassium hydroxide are mixed in a mass ratio of 20:1, the temperature is raised to 60°C, 4.2 times the mass of the hydrogen-containing compound is added to the hydroxy vinyl ether epoxy copolymer, the temperature is raised to 100°C, the pressure is 0.2MPa, the reaction is carried out for 1h, and then 10 times the mass of the hydrogen-containing compound is added to the hydroxy vinyl ether epoxy copolymer, the temperature is raised to 112°C, the reaction is continued for 3h, and then 0.11 times the mass of the hydrogen-containing compound is added to the potassium hydroxide, the temperature is lowered to 104°C, the dehydration reaction is carried out for 1h, 8 times the mass of the hydrogen-containing compound is added to the hydroxy vinyl ether epoxy copolymer and 2.1 times the mass of the hydrogen-containing compound is added to the ethylene oxide, the temperature is raised to 114°C, the pressure is 0.2MPa, the reaction is continued for 1h, vacuum degassing and the pH is adjusted to 4.5 with a 14% mass fraction of phosphoric acid solution to obtain a polyether polyol composition for polyurethane foaming.

[0037] Example 2

[0038] The preparation method of the polyether polyol composition for polyurethane foaming in this embodiment is as follows:

[0039] S1. Under a nitrogen atmosphere, diaminodiphenylmethane and diethanolamine were mixed and reacted uniformly, and then a 14% potassium hydroxide solution was added dropwise at a rate of 2 ml / min, the mass ratio of diaminodiphenylmethane, diethanolamine and potassium hydroxide was 19:21:2, the temperature was raised to 91 ° C, the reaction was continued for 7 hours, the pH was adjusted to 6.8 with 85% phosphoric acid, the temperature was raised to 100 ° C, vacuum dehydration was performed, and hot filtration was performed to obtain a benzyl alcohol amine derivative; under a nitrogen atmosphere, tetrahydrophthalic anhydride and a benzyl alcohol amine derivative were mixed in a mass ratio of 2:4, the temperature was raised to 83 ° C, and the mixture was stirred uniformly. A 14% potassium hydroxide solution with a mass fraction of 0.045 times the mass of tetrahydrophthalic anhydride was added dropwise at a rate of 2 ml / min, the temperature was raised to 115 ° C, the reaction was continued for 7 hours, the pH was adjusted to 6.8 with 85% phosphoric acid, vacuum dehydration was performed and filtration was performed to obtain hydroxyphthalimide;

[0040] S2. Oleic acid, acetic acid and concentrated sulfuric acid were mixed in a mass ratio of 110:5:1, heated to 45°C, reacted for 15 hours, and then 0.30 times the mass of oleic acid and 30% hydrogen peroxide by mass was added dropwise at a rate of 2 ml / min. The reaction temperature was controlled at 55°C and the reaction was continued for 5.5 hours. The mixture was hydrolyzed with deionized water and separated. The pH was then neutralized with sodium carbonate to 6.5, and the mixture was evaporated under reduced pressure to obtain hydroxylated oleic acid; hydroxylated oleic acid and maleic anhydride were mixed in a mass ratio of 100:2, heated to 145°C, reacted for 2.5 hours, 0.25 times the mass of hydroxylated oleic acid glycerol and 0.005 times the mass of hydroxylated oleic acid catalyst zinc oxide were added, heated to 210°C, reacted for 1.5 hours, and then reduced to 4 kPa. The reaction was continued for 2.5 hours, cooled to room temperature, diluted with methanol equal to the mass of hydroxylated oleic acid, centrifuged and evaporated to obtain an oil-based polyester polyol;

[0041] S3. The hydroxyphthalimide and oil-based polyester polyol were mixed in a mass ratio of 2:35 and stirred to obtain a hydrogen-containing compound;

[0042] S4. Under a nitrogen atmosphere, hydroxy vinyl ether, dialkyl maleate, ethanol and azobisisobutyronitrile were mixed in a mass ratio of 10:14:30:0.025, heated to 70 ° C, reacted for 6 hours, cooled and precipitated with methanol, filtered and dried in vacuo to obtain a hydroxy vinyl ether copolymer; the hydroxy vinyl ether copolymer, epichlorohydrin, toluene and catalyst tetrabutylammonium bromide were mixed in a mass ratio of 1:2.5:5:0.02, heated to 90 ° C, reacted for 3.5 hours, and then a 15% sodium hydroxide solution with a mass fraction of 1.15 times the mass of the hydroxy vinyl ether copolymer was added dropwise at a rate of 2 ml / min, cooled to 40 ° C, and the reaction was continued for 2.5 hours. The mixture was centrifuged and washed 1.5 times with a mass fraction of 25% dilute sulfuric acid, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain a hydroxy vinyl ether epoxy copolymer;

[0043] S5. Under a nitrogen atmosphere, the hydrogen-containing compound and potassium hydroxide are mixed in a mass ratio of 20:1.1, the temperature is raised to 65°C, 4.3 times the mass of the hydrogen-containing compound is added to the hydroxy vinyl ether epoxy copolymer, the temperature is raised to 101°C, the pressure is 0.3MPa, the reaction is carried out for 1.5h, and then 13 times the mass of the hydrogen-containing compound is added to the hydroxy vinyl ether epoxy copolymer, the temperature is raised to 114°C, the reaction is continued for 3.5h, and then 0.115 times the mass of the hydrogen-containing compound is added to the potassium hydroxide, the temperature is lowered to 105°C, the dehydration reaction is carried out for 1.5h, 9 times the mass of the hydrogen-containing compound is added to the hydroxy vinyl ether epoxy copolymer and 2.2 times the mass of the hydrogen-containing compound is added to the ethylene oxide, the temperature is raised to 115°C, the pressure is 0.3MPa, the reaction is continued for 1.5h, vacuum degassing and adjusting the pH to 5.0 with a 15% mass fraction of phosphoric acid solution to obtain a polyether polyol composition for polyurethane foaming.

[0044] Example 3

[0045] The preparation method of the polyether polyol composition for polyurethane foaming in this embodiment is as follows:

[0046] S1. Under a nitrogen atmosphere, diaminodiphenylmethane and diethanolamine were mixed and reacted uniformly, and then a 16% potassium hydroxide solution was added dropwise at a rate of 3 ml / min, the mass ratio of diaminodiphenylmethane, diethanolamine and potassium hydroxide was 20:21:2, the temperature was raised to 92 ° C, the reaction was continued for 8 hours, the pH was adjusted to 7.0 with 85% phosphoric acid, the temperature was raised to 100 ° C, vacuum dehydration was carried out, and hot filtration was performed to obtain a benzyl alcohol amine derivative; under a nitrogen atmosphere, tetrahydrophthalic anhydride and a benzyl alcohol amine derivative were mixed in a mass ratio of 2:5, the temperature was raised to 85 ° C, the temperature was raised to 85 ° C, and the temperature was raised to 120 ° C, the reaction was continued for 8 hours, the pH was adjusted to 7.0 with 85% phosphoric acid, vacuum dehydration was carried out and filtration was performed to obtain hydroxyphthalimide;

[0047] S2. Oleic acid, acetic acid, and concentrated sulfuric acid were mixed in a mass ratio of 120:5:1, heated to 50°C, reacted for 2 hours, and then 0.35 times the mass of oleic acid and 30% hydrogen peroxide by mass was added dropwise at a rate of 3 ml / min. The reaction temperature was controlled at 60°C and the reaction was continued for 6 hours. The mixture was hydrolyzed with deionized water and separated. The pH was then neutralized with sodium carbonate to 7, and the mixture was evaporated under reduced pressure to obtain hydroxylated oleic acid. Hydroxylated oleic acid and maleic anhydride were mixed in a mass ratio of 100:3, heated to 150°C, reacted for 3 hours, 0.3 times the mass of hydroxylated oleic acid glycerol and 0.006 times the mass of hydroxylated oleic acid as a catalyst zinc oxide were added, heated to 220°C, reacted for 2 hours, and then reduced to 5 kPa. The reaction was continued for 3 hours, cooled to room temperature, diluted with methanol equal to the mass of hydroxylated oleic acid, centrifuged, and evaporated to obtain an oil-based polyester polyol.

[0048] S3 hydroxyphthalimide and oil-based polyester polyol were mixed in a mass ratio of 2: 5 and stirred to obtain a hydrogen-containing compound;

[0049] S4. Under a nitrogen atmosphere, hydroxy vinyl ether, dialkyl maleate, ethanol and azobisisobutyronitrile were mixed in a mass ratio of 10:15:30:0.03, heated to 72 ° C, reacted for 7 hours, cooled and precipitated with methanol, filtered and dried in vacuo to obtain a hydroxy vinyl ether copolymer; a hydroxy vinyl ether copolymer, epichlorohydrin, toluene and catalyst tetrabutylammonium bromide were mixed in a mass ratio of 1:3:5:0.03, heated to 100 ° C, reacted for 4 hours, and then a 16% sodium hydroxide solution with a mass fraction of 1.2 times the mass of the hydroxy vinyl ether copolymer was added dropwise at a rate of 3 ml / min, cooled to 60 ° C, and continued to react for 3 hours. The mixture was centrifuged and washed three times with a mass fraction of 30% dilute sulfuric acid, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain a hydroxy vinyl ether epoxy copolymer;

[0050] S5. Under a nitrogen atmosphere, the hydrogen-containing compound and potassium hydroxide are mixed in a mass ratio of 20:1.2, the temperature is raised to 70°C, 4.4 times the mass of the hydrogen-containing compound is added to the hydroxy vinyl ether epoxy copolymer, the temperature is raised to 102°C, the pressure is 0.4 MPa, the reaction is carried out for 2 hours, and then 15 times the mass of the hydrogen-containing compound is added to the hydroxy vinyl ether epoxy copolymer, the temperature is raised to 115°C, the reaction is continued for 4 hours, and then 0.12 times the mass of the hydrogen-containing compound is added to the potassium hydroxide, the temperature is lowered to 107°C, the dehydration reaction is carried out for 2 hours, 10 times the mass of the hydrogen-containing compound is added to the hydroxy vinyl ether epoxy copolymer and 2.3 times the mass of the hydrogen-containing compound is added to the ethylene oxide, the temperature is raised to 117°C, the pressure is 0.4 MPa, the reaction is continued for 2 hours, vacuum degassing and the pH is adjusted to 5.5 with a 17% mass fraction of phosphoric acid solution to obtain a polyether polyol composition for polyurethane foaming.

[0051] Comparative Example 1

[0052] The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between the polyether polyol composition for polyurethane foaming and Example 2 is that the hydrogen-containing compound is only hydroxyphthalimide.

[0053] Comparative Example 2

[0054] The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between the polyether polyol composition for polyurethane foaming and Example 2 is that the hydrogen-containing compound is only a grease-based polyester polyol.

[0055] Comparative Example 3

[0056] The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between the polyether polyol composition for polyurethane foaming and Example 2 is that the hydrogen-containing compound includes a benzylalkanolamine derivative and a grease-based polyester polyol.

[0057] Comparative Example 4

[0058] The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between the polyether polyol composition for polyurethane foaming and Example 2 is that the hydroxy vinyl ether epoxy copolymer is prepared by ring-opening addition reaction of hydroxy vinyl ether and epichlorohydrin followed by ring-closing reaction.

[0059] Comparative Example 5

[0060] The preparation method of Comparative Example 5 is the same as that of Example 2. The difference between the polyether polyol composition for polyurethane foaming and Example 2 is that the polyether polyol composition for polyurethane foaming prepared in this example is prepared by reacting a hydrogen-containing compound with propylene oxide.

[0061] Effect Examples

[0062] Table 1 below shows the performance test results of the polyether polyol compositions for polyurethane foaming prepared in Examples and Comparative Examples;

[0063] Table 1

[0064]

[0065] From the comparison of the performance data in Table 1, it can be seen that the polyether polyol composition for polyurethane foaming prepared by the present invention not only has excellent mechanical strength and heat resistance, but also has moisture and heat resistance stability;

[0066] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 1, Comparative Example 2, Comparative Example 3, it can be found that the oil-based polyester polyol prepared by the reaction of hydroxylated oleic acid, maleic anhydride and glycerol, the benzyl alcohol amine derivative prepared by the reaction of diaminodiphenylmethane and diethanolamine, and the hydroxyphthalimide prepared by tetrahydrophthalic anhydride, the hydrogen-containing compound, the hydrogen-containing compound, the hydroxyphthalimide and the oil-based polyester polyol have good compatibility, and the cross-linked structure is formed by enhancing the hydrogen bonding effect between molecules, thereby improving the heat resistance and mechanical strength of the foamed polyurethane.

[0067] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 4, Comparative Example 5, it can be found that the polyether polyol composition made of hydroxyl vinyl ether epoxy copolymer and hydrogen-containing compound can form multiple rigid cross-linking structures of epoxy groups, hydroxyl groups and vinyl groups with isocyanate, which not only enhances the hardness and elasticity of the polyurethane foam, but also inhibits the hydrolysis of the polyurethane foam in a hot and humid environment, further improving the stability of the foamed polyurethane.

[0068] Obviously, the above embodiments are merely examples for the purpose of clearly illustrating the embodiments of the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will readily appreciate that other variations or modifications based on the above description are possible. It is not necessary and impossible to enumerate all embodiments here. However, such obvious variations or modifications arising from the spirit of the present invention remain within the scope of protection of the present invention.

Claims

1. A polyether polyol composition for polyurethane foaming, characterized in that The invention comprises a hydrogen-containing compound and a hydroxy vinyl ether epoxy copolymer; the hydrogen-containing compound comprises hydroxyphthalimide and an oil-based polyester polyol.

2. A polyether polyol composition for polyurethane foaming according to claim 1, characterized in that: The tetrahydrophthalic anhydride is prepared by reacting with a benzylalkanolamine derivative; the benzylalkanolamine derivative is prepared by reacting diaminodiphenylmethane with diethanolamine.

3. A polyether polyol composition for polyurethane foaming according to claim 1, characterized in that: The oil-based polyester polyol is prepared by reacting hydroxylated oleic acid, maleic anhydride and glycerol.

4. A polyether polyol composition for polyurethane foaming according to claim 1, characterized in that: The hydroxy vinyl ether epoxy copolymer is prepared by copolymerizing hydroxy vinyl ether with dialkyl maleate, and then performing ring-opening addition reaction with epichlorohydrin and then performing ring-closing reaction.

5. The method for preparing a polyether polyol composition for polyurethane foaming according to claim 1, wherein: The specific steps include: S1. Under a nitrogen atmosphere, tetrahydrophthalic anhydride and a benzyl alcohol amine derivative were mixed in a mass ratio of 2:3-5, heated to 82-85°C, stirred evenly, and then a 12-16% potassium hydroxide solution (0.03-0.06 times the mass of tetrahydrophthalic anhydride) was added dropwise at a rate of 1-3 ml / min. The mixture was heated to 110-120°C and reacted for 6-8 hours. The pH was adjusted to 6.5-7.0 with 85% phosphoric acid, vacuum dehydration was performed, and filtration was performed to obtain hydroxyphthalimide. S2. Mix hydroxylated oleic acid and maleic anhydride in a mass ratio of 100:1-3, heat to 140-150°C, react for 2-3 hours, add glycerol (0.2-0.3 times the mass of the hydroxylated oleic acid) and zinc oxide (0.004-0.006 times the mass of the hydroxylated oleic acid) as a catalyst, heat to 200-220°C, react for 1-2 hours, reduce pressure to 3-5 kPa, continue to react for 2-3 hours, cool to room temperature, dilute with methanol (an equal mass of the hydroxylated oleic acid), centrifuge, and rotary evaporate to obtain a grease-based polyester polyol. S3. The hydroxyphthalimide and oil-based polyester polyol were mixed and stirred to obtain a hydrogen-containing compound; S4. The hydroxy vinyl ether copolymer, epichlorohydrin, toluene and catalyst tetrabutylammonium bromide were mixed in a mass ratio of 1:2-3:5:0.01-0.03, heated to 80-100 ° C, reacted for 3-4 hours, and then a 14-16% sodium hydroxide solution of 1.1-1.2 times the mass of the hydroxy vinyl ether copolymer was added dropwise at a rate of 1-3 ml / min. The mixture was cooled to 30-60 ° C and the reaction was continued for 2-3 hours. The mixture was centrifuged and washed 1-3 times with a mass fraction of 20-30% dilute sulfuric acid, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain a hydroxy vinyl ether epoxy copolymer; S5. Under a nitrogen atmosphere, the hydrogen-containing compound and potassium hydroxide were mixed in a mass ratio of 20:1-1.2, the temperature was raised to 60-70°C, 4.2-4.4 times the mass of the hydrogen-containing compound of the hydroxy vinyl ether epoxy copolymer was added, the temperature was raised to 100-102°C, the pressure was 0.2-0.4 MPa, the reaction was carried out for 1-2 hours, and then 10-15 times the mass of the hydrogen-containing compound of the hydroxy vinyl ether epoxy copolymer was added, the temperature was raised to 112-115°C, the reaction was continued for 3-4 hours, and then 0. The method comprises the following steps of: adding 11 to 0.12 times the mass of potassium hydroxide, cooling to 104 to 107° C., dehydrating for 1 to 2 hours, adding 8 to 10 times the mass of the hydrogen-containing compound in terms of hydroxy vinyl ether epoxy copolymer and 2.1 to 2.3 times the mass of the hydrogen-containing compound in terms of ethylene oxide, heating to 114 to 117° C., and keeping the pressure at 0.2 to 0.4 MPa, continuing the reaction for 1 to 2 hours, vacuum degassing, and adjusting the pH to 4.5 to 5.5 with a phosphoric acid solution with a mass fraction of 14 to 17%, to obtain a polyether polyol composition for polyurethane foaming.

6. The method for preparing a polyether polyol composition for polyurethane foaming according to claim 5, wherein: In the above step S1, the preparation method of the benzyl alcohol amine derivative is as follows: under a nitrogen atmosphere, diaminodiphenylmethane and diethanolamine are mixed and reacted uniformly, and then a potassium hydroxide solution with a mass fraction of 12 to 16% is added dropwise at a rate of 1 to 3 ml / min, and the mass ratio of diaminodiphenylmethane, diethanolamine and potassium hydroxide is 18 to 20:21:

2. The temperature is raised to 90 to 92 ° C. and the reaction is carried out for 6 to 8 hours. The pH is adjusted to 6.5 to 7.0 with 85% phosphoric acid by mass, and the temperature is raised to 100 ° C. Vacuum dehydration is carried out, and hot filtration is performed to obtain the benzyl alcohol amine derivative.

7. The method for preparing a polyether polyol composition for polyurethane foaming according to claim 5, wherein: In step S2 above, the preparation method of hydroxylated oleic acid is as follows: oleic acid, acetic acid and concentrated sulfuric acid are mixed in a mass ratio of 100-120:5:1, heated to 40-50°C, reacted for 1-2 hours, and then 0.25-0.35 times the mass of oleic acid and 30% hydrogen peroxide are added dropwise at a rate of 1-3 ml / min. The reaction temperature is controlled at 50-60°C, and the reaction is continued for 5-6 hours. The oleic acid is hydrolyzed with deionized water and separated, and then neutralized with sodium carbonate to a pH of 6-7, and vacuum rotary evaporation is performed to obtain hydroxylated oleic acid.

8. The method for preparing a polyether polyol composition for polyurethane foaming according to claim 5, wherein: In the above step S3, the mass ratio of hydroxyphthalimide to oil-based polyester polyol is 2:2-5.

9. The method for preparing a polyether polyol composition for polyurethane foaming according to claim 5, wherein: In the above step S4, the preparation method of the hydroxy vinyl ether copolymer is as follows: under a nitrogen atmosphere, hydroxy vinyl ether, dialkyl maleate, ethanol and azobisisobutyronitrile are mixed in a mass ratio of 10:13 to 15:30:0.02 to 0.03, heated to 68 to 72°C, reacted for 5 to 7 hours, cooled, precipitated with methanol, filtered, and vacuum dried to obtain a hydroxy vinyl ether copolymer.

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