Polyurethane foam material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of thermal insulation materials, and discloses a polyurethane foam material and a preparation method and application thereof, the polyurethane foam material is prepared from a raw material composition containing polyol, isocyanate, a catalyst, a polymer microsphere emulsion and a filler; the filler contains one or more than two of aerogel, fumed silica and polymer microspheres; the polymer microsphere emulsion is prepared by adopting a soap-free emulsion polymerization method, the preparation raw materials of the polymer microsphere emulsion comprise an oleophylic polymeric monomer and an amphiphilic polymeric monomer, and the polymer microsphere is prepared by drying the polymer microsphere emulsion. According to the invention, the polymer microsphere emulsion is used as a foaming agent, and the polymer emulsion does not contain fluorine and a traditional surfactant, so that the prepared polyurethane foam material is low in heat conductivity coefficient and density, good in heat preservation and heat insulation performance and environment-friendly, and meanwhile, the strength of polyurethane foam can also be improved; by adding the filler, the heat conductivity coefficient of the polyurethane foam material can be further reduced, and the thermal insulation performance of the polyurethane foam material is improved.

Description

Technical Field

[0001] The invention relates to the technical field of foamed heat-insulating materials, and in particular to a polyurethane foam material and a preparation method and application thereof. Background Art

[0002] With the development of industrial society, people's production and life are increasingly inseparable from energy, but this is accompanied by a series of problems such as high carbon emissions. Thermal insulation during pipeline transportation is of great significance to energy conservation, and the preparation and development of high-performance environmentally friendly thermal insulation materials are crucial. At present, commonly used thermal insulation building materials include expanded polystyrene board (EPS), extruded polystyrene board (XPS), spray polyurethane (SPU) and polystyrene particles, etc. Auxiliary materials are polymer bonding mortar, interface treatment agent or interface mortar, special expansion screws, alkali-resistant glass fiber mesh and galvanized steel wire mesh.

[0003] Polyurethane, whose full name is polyurethane, is a polymer compound. It was first produced by Otto Bayer in 1937. Polyurethane has two major types: polyester type and polyether type. They can be made into polyurethane plastics (mainly polyurethane foam), polyurethane fibers (i.e. spandex), polyurethane rubber and elastomers.

[0004] Polyurethane foam is widely used in thermal insulation, sound insulation and noise reduction due to its advantages such as light weight, low thermal conductivity, excellent sound insulation and noise reduction, high compression strength and good dimensional stability. However, while polyurethane foam brings convenience to people, it also has some hidden dangers. At present, fluorine-containing foaming agents or pure water are usually used in the polyurethane foaming process. Among them, the fluorine-containing compounds in the fluorine-containing foaming agent have great damage to the environment. At the same time, they have strong thermal stability and acid and alkali resistance, are not easy to decompose, and are easily enriched in the food chain, posing a great threat to human health. The polyurethane foam material foamed with pure water is more environmentally friendly, but the polyurethane foam prepared by this method has problems such as uneven foaming pore size and poor mechanical properties. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems in the prior art that the foaming agent used in the polyurethane foam foaming process is not environmentally friendly or has poor foaming performance, and to provide a polyurethane foam material and a preparation method and application thereof.

[0006] In order to achieve the above object, the present invention provides a polyurethane foam material, which is made of a raw material composition containing polyol, isocyanate, catalyst, polymer microsphere emulsion and filler;

[0007] Wherein, the filler contains one or more of aerogel, fumed silica and polymer microspheres;

[0008] The polymer microsphere emulsion is prepared by soap-free emulsion polymerization. Its preparation raw materials contain lipophilic polymerization monomers and amphiphilic polymerization monomers. The polymer microspheres are prepared by drying the polymer microsphere emulsion.

[0009] Preferably, the polymer microsphere emulsion is prepared according to the following process:

[0010] The amphiphilic polymerizable monomer and water are mixed and stirred, and then a water-soluble initiator and a lipophilic polymerizable monomer are added to react.

[0011] Preferably, the weight ratio of the lipophilic polymerizable monomer, the amphiphilic polymerizable monomer and the water-soluble initiator is 10:1-6:0.2-1.

[0012] Preferably, the reaction conditions include: temperature of 70-90° C. and time of 3-5 h.

[0013] Preferably, the water-soluble initiator is potassium persulfate and / or ammonium persulfate.

[0014] Preferably, the lipophilic polymerizable monomer is selected from one or more of styrene, 4-methylstyrene, 4-tert-butylstyrene, methyl acrylate, methyl methacrylate, butyl acrylate, isooctyl acrylate and isooctyl methacrylate.

[0015] Preferably, the amphiphilic polymerizable monomer is acrylic acid and / or acrylamide.

[0016] Preferably, the density of the aerogel is 30 to 50 kg / m 3 , porosity>90%, specific surface area 500~650m 2 / g.

[0017] Preferably, the density of the fumed silica is 55 to 60 kg / m 3 , specific surface area 380~400m 2 / g.

[0018] Preferably, the polyol is polypropylene glycol and / or polytetramethylene glycol.

[0019] Preferably, the isocyanate is one or more of isophorone diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate.

[0020] Preferably, the catalyst is selected from one or more of triethylenediamine, bis(dimethylaminoethyl) ether, stannous octoate, tin naphthenate and dibutyltin dilaurate.

[0021] Preferably, the weight ratio of the polyol to the isocyanate is 100:45-70.

[0022] A second aspect of the present invention provides a method for preparing a polyurethane foam material, the method comprising the following steps:

[0023] (1) heating and dehydrating the polyol, and then mixing and reacting the polyol with isocyanate to obtain a prepolymer having an isocyanate content of 5 to 10%;

[0024] (2) mixing the prepolymer and the filler to obtain a premix;

[0025] (3) mixing the premix with the polymer microsphere emulsion and the catalyst, and then foaming and ripening;

[0026] The filler contains one or more of aerogel, fumed silica and polymer microspheres.

[0027] Preferably, in step (1), the heating dehydration process comprises: heating the polyol to 100-110° C. and dehydrating the polyol under a vacuum degree of -0.07 to -0.1 MPa for 2 to 3 hours.

[0028] Preferably, in step (1), the reaction conditions include: temperature of 75-95° C. and time of 3-4 h.

[0029] Preferably, in step (1), the weight ratio of the polyol to the isocyanate is 100:45-70.

[0030] Preferably, in step (2), the weight ratio of the prepolymer to the filler is 15:0.1-1.

[0031] Preferably, in step (3), the weight ratio of the premix, the polymer microsphere emulsion and the catalyst is 15:0.1 to 1:0.1 to 0.5.

[0032] Preferably, in step (3), the foaming conditions include: temperature of 20 to 30° C. and time of 5 to 15 hours.

[0033] Preferably, in step (3), the aging conditions include: a temperature of 20 to 30° C. and a time of 48 to 100 hours.

[0034] Preferably, the method further comprises preparing the polymer microsphere emulsion according to the following steps: mixing and stirring the amphiphilic polymer monomer and water, and then adding a water-soluble initiator and a lipophilic polymer monomer to react.

[0035] Preferably, the weight ratio of the lipophilic polymerizable monomer, the amphiphilic polymerizable monomer and the water-soluble initiator is 10:1-6:0.2-1.

[0036] Preferably, when preparing the polymer microsphere emulsion, the reaction conditions include: temperature of 70 to 90° C. and time of 3 to 5 hours.

[0037] Preferably, the water-soluble initiator is potassium persulfate and / or ammonium persulfate.

[0038] Preferably, the lipophilic polymerizable monomer is selected from one or more of styrene, 4-methylstyrene, 4-tert-butylstyrene, methyl acrylate, methyl methacrylate, butyl acrylate, isooctyl acrylate and isooctyl methacrylate.

[0039] Preferably, the amphiphilic polymerizable monomer is acrylic acid and / or acrylamide.

[0040] Preferably, the polyol is polypropylene glycol and / or polytetramethylene glycol.

[0041] Preferably, the isocyanate is one or more of isophorone diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate.

[0042] Preferably, the catalyst is selected from one or more of triethylenediamine, bis(dimethylaminoethyl) ether, stannous octoate, tin naphthenate and dibutyltin dilaurate.

[0043] The third aspect of the present invention provides a polyurethane foam material prepared by the method as described above.

[0044] A fourth aspect of the present invention provides a use of the polyurethane foam material as described above in the preparation of thermal insulation products.

[0045] In the technical solution provided by the present invention, a polymer microsphere emulsion prepared by a soap-free emulsion polymerization method is used as a foaming agent. The polymer microsphere emulsion does not contain fluorine and traditional surfactants and is harmless to the environment and human body, so that the prepared polyurethane foam material not only has low thermal conductivity and density, good thermal insulation performance, but also is environmentally friendly. At the same time, after foaming, the polymer microspheres therein adhere to the pore walls, thereby improving the strength of the polyurethane foam material; by adding fillers, the micropores and mesopore structures in the polyurethane foam can be increased, thereby further reducing the thermal conductivity and density of the polyurethane foam material, and improving its thermal insulation performance and mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 are photographs of the polymer microsphere emulsions prepared in Examples 1-4 of the present invention;

[0047] Figure 2 1 is a graph showing the particle size test results of the polymer microspheres prepared in Examples 1-4 of the present invention;

[0048] Figure 3 is a photograph of the polymer microspheres prepared in Example 2-3 of the present invention;

[0049] Figure 4 is a scanning electron microscope image of the polymer microsphere emulsion prepared in Example 1 of the present invention;

[0050] Figure 5 is a scanning electron microscope image of the polymer microsphere emulsion prepared in Example 2 of the present invention;

[0051] Figure 6 is a scanning electron microscope image of the polymer microsphere emulsion prepared in Example 3 of the present invention;

[0052] Figure 7 is a scanning electron microscope image of the polymer microsphere emulsion prepared in Example 4 of the present invention;

[0053] Figure 8 It is a graph showing the compression performance test results of the polyurethane foam materials prepared in Examples 1-5 of the present invention and Comparative Examples 1-2. DETAILED DESCRIPTION

[0054] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0055] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0056] At present, there are some problems with the commonly used foaming agents in the preparation of polyurethane foam materials. Among them, high-performance foaming agents contain fluorine, which is very harmful to the human body and the environment; using pure water as a foaming agent cannot obtain a low-density and uniformly porous polyurethane foam material, and its thermal insulation and mechanical properties are poor.

[0057] In view of this, the present invention provides a polyurethane foam material, which is made of a raw material composition containing polyol, isocyanate, catalyst, polymer microsphere emulsion and filler; wherein the filler contains one or more of aerogel, fumed silica and polymer microspheres; the polymer microsphere emulsion is prepared by soap-free emulsion polymerization, and its preparation raw materials contain lipophilic polymerization monomers and amphiphilic polymerization monomers, and the polymer microspheres are prepared by drying the polymer microsphere emulsion.

[0058] In the present invention, polymer microsphere emulsion is used as a foaming agent, which is more environmentally friendly than fluorine-containing foaming agents; compared with pure water as a foaming agent, the foam pore size of the prepared polyurethane foam material is more uniform and fine. The present invention uses polymer microsphere emulsion as a foaming agent, so that a polyurethane foam material with uniform and fine foaming can be prepared without fluorine.

[0059] The polyurethane foam material provided by the present invention is not only harmless to the environment and human body and has good environmental protection, but also has low thermal conductivity and density and good thermal insulation performance. At the same time, after foaming, the polymer microspheres therein adhere to the pore walls, thereby improving the strength of the polyurethane foam material; by adding fillers, the micropores and mesoporous structures in the polyurethane foam can be increased, thereby further reducing the thermal conductivity and density of the polyurethane foam material, and improving its thermal insulation performance and mechanical properties.

[0060] In a specific embodiment, the polymer microsphere emulsion is prepared according to the following process: an amphiphilic polymer monomer and water are mixed and stirred, and then a water-soluble initiator and a lipophilic polymer monomer are added to react.

[0061] In a preferred embodiment, the water-soluble initiator is added in batches.

[0062] In a preferred embodiment, the weight ratio of the lipophilic polymerizable monomer, the amphiphilic polymerizable monomer and the water-soluble initiator is 10:1-6:0.2-1, more preferably 10:1-5:0.3-0.6.

[0063] In a preferred embodiment, the reaction conditions include: temperature of 70-90° C. and time of 3-5 h.

[0064] Further preferably, the polymer microsphere emulsion is prepared according to the following process: adding lipophilic polymerization monomers into deionized water, stirring to dissolve, placing the obtained solution in a three-necked flask, heating to 70-90°C, then adding lipophilic polymerization monomers and part of the water-soluble initiator to react, and adding the water-soluble initiator after 1h and 2h of the reaction.

[0065] In a preferred embodiment, the lipophilic polymerizable monomer is selected from one or more of styrene, 4-methylstyrene, 4-tert-butylstyrene, methyl acrylate, methyl methacrylate, butyl acrylate, isooctyl acrylate and isooctyl methacrylate, preferably a mixture of styrene and isooctyl acrylate.

[0066] In a preferred embodiment, the amphiphilic polymerizable monomer is acrylic acid and / or acrylamide.

[0067] When the lipophilic polymerizable monomer is a mixture of styrene and isooctyl acrylate, preferably, the content of the styrene is not less than 40 wt % based on the total weight of the styrene and isooctyl acrylate.

[0068] It should be noted that the selection of the polymer microsphere emulsion and the polymer microspheres are independent of each other. In some specific embodiments, the lipophilic monomer for preparing the polymer microsphere emulsion is a mixture of styrene and isooctyl acrylate, and the lipophilic polymerized monomer for preparing the polymer microspheres is styrene. In a preferred embodiment, the lipophilic polymerized monomer for preparing the polymer microspheres is styrene, so that the obtained polymer microspheres have better dispersibility.

[0069] In a preferred embodiment, the water-soluble initiator is potassium persulfate and / or ammonium persulfate.

[0070] In a preferred embodiment, the polymer microspheres are obtained by freeze-drying the polymer microsphere emulsion. In a specific implementation, the polymer microsphere emulsion is dried in a freeze dryer to obtain powder to obtain the polymer microspheres.

[0071] In a preferred embodiment, the density of the aerogel is 30 to 50 kg / m 3 , porosity>90%, specific surface area 500~650m 2 / g.

[0072] In a preferred embodiment, the density of the fumed silica is 55 to 60 kg / m 3 , specific surface area 380~400m 2 / g.

[0073] In a preferred embodiment, the filler is a mixture of aerogel, fumed silica and polymer microspheres. Through the synergistic effect of the three, the thermal conductivity of the prepared polyurethane foam material is lower, and the thermal insulation and mechanical properties are better.

[0074] In a preferred embodiment, the polyol is polypropylene glycol (PPG) and / or polytetramethylene glycol (PTMG). More preferably, the molecular weight of the polypropylene glycol is 800-1200, and the molecular weight of the polytetramethylene glycol is 800-1200.

[0075] In a preferred embodiment, the isocyanate is selected from one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI).

[0076] In a preferred embodiment, the catalyst is selected from one or more of triethylenediamine, bis(dimethylaminoethyl) ether, stannous octoate, tin naphthenate and dibutyltin dilaurate.

[0077] In a preferred embodiment, the weight ratio of the polyol to the isocyanate is 100:45-70, preferably 100:50-60.

[0078] The present invention also provides a method for preparing a polyurethane foam material, which comprises the following steps:

[0079] (1) heating and dehydrating the polyol, and then mixing and reacting the polyol with isocyanate to obtain a prepolymer having an isocyanate content of 5 to 10%;

[0080] (2) mixing the prepolymer and the filler to obtain a premix;

[0081] (3) The premix is ​​mixed with the polymer microsphere emulsion and the catalyst, and then foamed and matured.

[0082] In order to improve the molding and performance of the obtained polyurethane foam material, in the present invention, the polyol is decolorized at 100-110°C and vacuum negative pressure. Preferably, in step (1), the heating and dehydration process comprises: heating the polyol to 100-110°C and vacuuming the polyol to a temperature of -0.07-

[0083] Dehydrate at -0.1MPa for 2 to 3 hours.

[0084] In the present invention, in step (1), the isocyanate (NCO) content is measured by di-n-butylamine back titration method.

[0085] In the present invention, the amount of polyol and isocyanate used in step (1) is not limited, nor is the reaction conditions. It is sufficient as long as the isocyanate content in the obtained prepolymer is controlled to be 5-10%.

[0086] In a preferred embodiment, in step (1), the reaction conditions include: temperature of 75-95° C. and time of 3-4 h.

[0087] In a preferred embodiment, in step (1), the weight ratio of the polyol to the isocyanate is 100:45-70, preferably 100:50-60.

[0088] In a preferred embodiment, in step (1), the polyol is polypropylene glycol (PPG) and / or polytetramethylene glycol (PTMG). More preferably, the molecular weight of the polypropylene glycol is 800-1200, and the molecular weight of the polytetramethylene glycol is 800-1200.

[0089] In a preferred embodiment, in step (1), the isocyanate is selected from one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI).

[0090] In the method of the present invention, in step (2), the filler contains one or more of aerogel, fumed silica and polymer microspheres. Among them, polymer microspheres are beneficial to the support of the pore walls in the polyurethane foam, and aerogel and fumed silica are beneficial to increase the mesopore and micropore structure in the polyurethane foam.

[0091] In a preferred embodiment, in step (2), the density of the aerogel is 30 to 50 kg / m 3 , porosity>90%, specific surface area 500~650m 2 / g.

[0092] In a preferred embodiment, in step (2), the density of the fumed silica is 55 to 60 kg / m 3 , specific surface area 380~400m 2 / g.

[0093] In a preferred embodiment, in step (2), the filler is a mixture of aerogel, fumed silica and polymer microspheres. Through the synergistic effect of the three, the thermal conductivity of the prepared polyurethane foam material is lower, and the thermal insulation and mechanical properties are better.

[0094] In a preferred embodiment, in step (2), the weight ratio of the prepolymer to the filler is 15:0.1-1, preferably 15:0.2-0.6.

[0095] In a preferred embodiment, the method further comprises preparing the polymer microsphere emulsion according to the following steps: mixing and stirring the amphiphilic polymer monomer and water, then adding a water-soluble initiator and a lipophilic polymer monomer, and reacting at 70 to 90° C. for 3 to 5 hours.

[0096] In a preferred embodiment, the water-soluble initiator is added in batches.

[0097] In a preferred embodiment, the weight ratio of the lipophilic polymerizable monomer, the amphiphilic polymerizable monomer and the water-soluble initiator is 10:1-6:0.2-1, more preferably 10:1-5:0.3-0.6.

[0098] In a preferred embodiment, the lipophilic polymerizable monomer is selected from one or more of styrene, 4-methylstyrene, 4-tert-butylstyrene, methyl acrylate, methyl methacrylate, butyl acrylate, isooctyl acrylate and isooctyl methacrylate, preferably a mixture of styrene and isooctyl acrylate.

[0099] When the lipophilic polymerizable monomer is a mixture of styrene and isooctyl acrylate, preferably, the content of the styrene is not less than 40 wt % based on the total weight of the styrene and isooctyl acrylate.

[0100] In a preferred embodiment, the amphiphilic polymerizable monomer is acrylic acid and / or acrylamide.

[0101] In a preferred embodiment, the water-soluble initiator is potassium persulfate and / or ammonium persulfate.

[0102] In a preferred embodiment, the method further comprises preparing the polymer microspheres according to the following steps: freeze-drying the polymer microsphere emulsion. In specific implementation, the polymer microsphere emulsion is dried in a freeze dryer to obtain powder to obtain polymer microspheres.

[0103] In a preferred embodiment, in step (3), the weight ratio of the premix, the polymer microsphere emulsion and the catalyst is 15:0.1-1:0.1-0.5, preferably 15:0.2-0.5:0.15-0.35.

[0104] In a preferred embodiment, in step (3), the catalyst is selected from one or more of triethylenediamine, bis(dimethylaminoethyl) ether, stannous octoate, tin naphthenate and dibutyltin dilaurate.

[0105] In a preferred embodiment, in step (3), the foaming conditions include: temperature of 20 to 30° C., preferably 22 to 28° C.; time of 5 to 15 hours, preferably 8 to 12 hours.

[0106] In a preferred embodiment, the aging conditions include: a temperature of 20 to 30° C., preferably 22 to 28° C.; and a time of 48 to 100 hours, preferably 60 to 80 hours.

[0107] The present invention also provides a polyurethane foam material prepared by the method as described above.

[0108] The polyurethane foam material provided by the present invention, by adding soap-free polymer microsphere emulsion and fillers such as aerogel, fumed silica, polymer microspheres, etc., ensures the environmental friendliness of the material while taking into account the low density and low thermal conductivity of the material. It can be applied to various scenarios such as medium-temperature and low-temperature pipeline transportation, building wall insulation, etc., has great practical significance for reducing heat loss and saving energy, and has a relatively broad application prospect.

[0109] The present invention also proposes the use of the polyurethane foam material as described above in the preparation of thermal insulation products. Since the polyurethane foam material has good thermal insulation performance, the thermal insulation products prepared therefrom have good competitive advantages. The present invention does not limit the specific types of the thermal insulation products, which may be daily necessities, building materials, etc.

[0110] The present invention will be described in detail below through examples, but the protection scope of the present invention is not limited thereto.

[0111] In the following examples and comparative examples, room temperature refers to 25°C.

[0112] In the following examples and comparative examples, unless otherwise specified, all are commercially available products.

[0113] Aerogel, purchased from Guangdong Alison Technology Co., Ltd., with a density of 40 kg / m 3 , porosity>90%, specific surface area 500~650m 2 / g.

[0114] Fumed silica, purchased from Hubei Huifu Nanomaterials Co., Ltd., with a density of 55-60 kg / m 3 , specific surface area 380~400m 2 / g.

[0115] In the following examples and comparative examples, the test methods involved are as follows:

[0116] Isocyanate (NCO) content: measured by di-n-butylamine back titration method, the specific steps are: use 0.5 mol / L sodium carbonate standard substance aqueous solution to calibrate the prepared hydrochloric acid aqueous solution, use this calibrated hydrochloric acid solution to calibrate the di-n-butylamine toluene solution (26g di-n-butylamine is added to 160mL toluene, and an appropriate amount of isopropanol is added to assist dissolution). Accurately weigh 2-3g of prepolymer sample, quantitatively add 20mL di-n-butylamine, stir and react for 30 minutes, use hydrochloric acid solution to titrate the unreacted di-n-butylamine, and determine the isocyanate content in the prepolymer by subtraction.

[0117] Density test: Use a cylindrical mold with a fixed bottom area for foaming, measure the thickness after foaming, and calculate the total foaming volume. Take out the foamed material and weigh it. The ratio of the mass to the volume of the foamed material is recorded as the density.

[0118] Thermal conductivity test: The thermal conductivity of the foam material was tested using the KDRX-Ⅱ transient fast line method thermal conductivity tester produced by Xiangtan Xiangyi Instrument Co., Ltd. The test was performed three times to obtain the average value.

[0119] Compression strength test: Use INSTRON universal testing machine to test the compression performance of the material.

[0120] Example 1

[0121] The preparation method of the polymer microsphere emulsion and the polymer microsphere comprises the following steps:

[0122] Weigh 10 parts by weight of styrene and mix them evenly; add 1 part by weight of acrylamide to 700 parts by weight of deionized water, stir to dissolve, place in a three-necked flask, heat to 80° C., add 0.1 parts by weight of potassium persulfate, drop styrene into the three-necked flask, add 0.1 parts by weight of potassium persulfate after the reaction is carried out for 1 hour and 2 hours respectively, react for 4 hours, and obtain a uniform white emulsion, i.e., a polymer microsphere emulsion;

[0123] The polymer microsphere emulsion is dried in a freeze dryer to obtain powder, thereby obtaining polymer microspheres.

[0124] The preparation method of polyurethane foam material comprises the following steps:

[0125] (1) 100 parts by weight of polytetrahydrofuran polyol (PTMG1000) were weighed and added to a clean three-necked flask, which was slowly heated to 105° C. under stirring, and dehydrated under vacuum negative pressure (−0.095 MPa) for 3 h. After the temperature was lowered to 50° C., 51 parts by weight of isophorone diisocyanate were added, and the temperature was raised to 85° C. and kept warm for 4 h. The isocyanate content was tested to be 6.1%, thereby obtaining a prepolymer;

[0126] (2) Weigh 15 parts by weight of the prepolymer into a beaker, add 0.1 parts by weight of fumed silica, 0.1 parts by weight of aerogel and 0.1 parts by weight of polymer microspheres at a stirring speed of 600 rpm, and stir thoroughly to obtain a milky white premix;

[0127] (3) Weigh 15 parts by weight of the premix, add 0.3 parts by weight of the polymer microsphere emulsion and 0.2 parts by weight of dibutyltin dilaurate at a stirring speed of 600 rpm, mix thoroughly and pour into a mold, foam at room temperature for 10 hours to set, and mature at room temperature for 72 hours to obtain a polyurethane foam material.

[0128] Example 2

[0129] The method described in Example 1 is used for implementation, except that the oleophilic polymer monomer is obtained by mixing 8 parts by weight of styrene and 2 parts by weight of isooctyl acrylate.

[0130] Specifically, the preparation method of the polymer microsphere emulsion and the polymer microsphere comprises the following steps:

[0131] Weigh 8 parts by weight of styrene and 2 parts by weight of isooctyl acrylate, mix them evenly, and obtain a lipophilic mixed monomer, that is, based on the total weight of the styrene and isooctyl acrylate, the content of the styrene is 80wt%; add 1 part by weight of acrylamide to 700 parts by weight of deionized water, stir to dissolve, place in a three-necked flask, heat to 80° C., add 0.1 parts by weight of potassium persulfate, dropwise add the lipophilic mixed monomer into the three-necked flask, add 0.1 parts by weight of potassium persulfate after the reaction is carried out for 1 hour and 2 hours respectively, react for 4 hours, and obtain a uniform white emulsion, that is, a polymer microsphere emulsion;

[0132] The polymer microsphere emulsion is dried in a freeze dryer to obtain powder, thereby obtaining polymer microspheres.

[0133] The preparation method of polyurethane foam material comprises the following steps:

[0134] (1) 100 parts by weight of polytetrahydrofuran polyol were weighed and added to a clean three-necked flask, which was slowly heated to 105° C. under stirring, and dehydrated at a vacuum negative pressure (-0.095 MPa) for 3 hours. After the temperature was cooled to 50° C., 51 parts by weight of isophorone diisocyanate were added, and the temperature was raised to 85° C. and kept warm for 4 hours. The isocyanate content was tested to be 6.1%, thereby obtaining a prepolymer.

[0135] (2) Weigh 15 parts by weight of the prepolymer into a beaker, add 0.1 parts by weight of fumed silica, 0.1 parts by weight of aerogel, and 0.1 parts by weight of polymer microspheres at a stirring speed of 600 rpm, and stir thoroughly to obtain a milky white premix.

[0136] (3) Weigh 15 parts by weight of the premix, add 0.3 parts of the polymer microsphere emulsion and 0.2 parts of dibutyltin dilaurate at a stirring speed of 600 rpm, mix thoroughly and pour into a mold, foam at room temperature for 10 hours to set, and mature at room temperature for 3 days to obtain a polyurethane foam material.

[0137] Example 3

[0138] The preparation method of polymer microsphere emulsion comprises the following steps:

[0139] 6 parts by weight of styrene and 4 parts by weight of isooctyl acrylate are weighed and mixed uniformly to obtain a lipophilic mixed monomer, that is, based on the total weight of the styrene and isooctyl acrylate, the content of the styrene is 60wt%; 1 part by weight of acrylamide is added to 700 parts by weight of deionized water, stirred to dissolve, placed in a three-necked flask, heated to 80° C., 0.1 parts by weight of potassium persulfate are added, the lipophilic mixed monomer is dripped into the three-necked flask, 0.1 parts by weight of potassium persulfate are added after the reaction is carried out for 1 hour and 2 hours respectively, and the reaction is carried out for 4 hours to obtain a uniform white emulsion, that is, a polymer microsphere emulsion.

[0140] The polymer microspheres are the polymer microspheres prepared in Example 1 (the lipophilic polymer monomer is pure styrene).

[0141] The preparation method of polyurethane foam material comprises the following steps:

[0142] (1) 100 parts by weight of polytetrahydrofuran polyol (PTMG1000) were weighed and added to a clean three-necked flask, which was slowly heated to 105° C. under stirring, and dehydrated under vacuum negative pressure (−0.095 MPa) for 3 h. After the temperature was lowered to 50° C., 51 parts by weight of isophorone diisocyanate were added, and the temperature was raised to 85° C. and kept warm for 4 h. The isocyanate content was tested to be 6.1%, thereby obtaining a prepolymer;

[0143] (2) Weigh 15 parts by weight of the prepolymer into a beaker, add 0.1 parts by weight of fumed silica, 0.1 parts by weight of aerogel, and 0.1 parts by weight of polymer microspheres whose lipophilic monomer is pure styrene obtained in Example 1 at a stirring speed of 600 rpm, and stir thoroughly to obtain a milky white premix;

[0144] (3) Weigh 15 parts by weight of the premix, add 0.3 parts by weight of the polymer microsphere emulsion and 0.2 parts by weight of dibutyltin dilaurate at a stirring speed of 600 rpm, mix thoroughly and pour into a mold, foam at room temperature for 10 hours to set, and mature at room temperature for 72 hours to obtain a polyurethane foam material.

[0145] Example 4

[0146] The preparation method of polymer microsphere emulsion comprises the following steps:

[0147] 4 parts by weight of styrene and 6 parts by weight of isooctyl acrylate are weighed and mixed uniformly to obtain a lipophilic mixed monomer, that is, based on the total weight of the styrene and isooctyl acrylate, the content of the styrene is 40wt%; 1 part by weight of acrylamide is added to 700 parts by weight of deionized water, stirred to dissolve, placed in a three-necked flask, heated to 80° C., 0.1 parts by weight of potassium persulfate are added, the lipophilic mixed monomer is dripped into the three-necked flask, 0.1 parts by weight of potassium persulfate are added after the reaction is carried out for 1 hour and 2 hours respectively, and the reaction is carried out for 4 hours to obtain a uniform white emulsion, that is, a polymer microsphere emulsion.

[0148] The polymer microspheres are the polymer microspheres prepared in Example 1 (the lipophilic polymer monomer is pure styrene).

[0149] The preparation method of polyurethane foam material comprises the following steps:

[0150] (1) 100 parts by weight of polytetrahydrofuran polyol (PTMG1000) were weighed and added to a clean three-necked flask, which was slowly heated to 105° C. under stirring, and dehydrated under vacuum negative pressure (−0.095 MPa) for 3 h. After the temperature was lowered to 50° C., 51 parts by weight of isophorone diisocyanate were added, and the temperature was raised to 85° C. and kept warm for 4 h. The isocyanate content was tested to be 6.1%, thereby obtaining a prepolymer;

[0151] (2) Weigh 15 parts by weight of the prepolymer into a beaker, add 0.1 parts by weight of fumed silica, 0.1 parts by weight of aerogel, and 0.1 parts by weight of polymer microspheres whose lipophilic monomer is pure styrene obtained in Example 1 at a stirring speed of 600 rpm, and stir thoroughly to obtain a milky white premix;

[0152] (3) Weigh 15 parts by weight of the premix, add 0.3 parts by weight of the polymer microsphere emulsion and 0.2 parts by weight of dibutyltin dilaurate at a stirring speed of 600 rpm, mix thoroughly and pour into a mold, foam at room temperature for 10 hours to set, and mature at room temperature for 72 hours to obtain a polyurethane foam material.

[0153] Example 5

[0154] The method described in Example 1 was followed, except that no polymer microspheres were added.

[0155] The specific steps include:

[0156] (1) 100 parts by weight of polytetrahydrofuran polyol (PTMG1000) were weighed and added to a clean three-necked flask, which was slowly heated to 105° C. under stirring, and dehydrated under vacuum negative pressure (−0.095 MPa) for 3 h. After the temperature was lowered to 50° C., 51 parts by weight of isophorone diisocyanate were added, and the temperature was raised to 85° C. and kept warm for 4 h. The isocyanate content was tested to be 6.1%, thereby obtaining a prepolymer;

[0157] (2) Weigh 15 parts by weight of the prepolymer into a beaker, add 0.1 parts by weight of fumed silica and 0.1 parts by weight of aerogel at a stirring speed of 600 rpm, and stir thoroughly to obtain a milky white premix;

[0158] (3) Weigh 15 parts by weight of the premix, add 0.3 parts by weight of the polymer microsphere emulsion prepared in Example 1 and 0.2 parts by weight of dibutyltin dilaurate at a stirring speed of 600 rpm, mix thoroughly and pour into a mold, foam at room temperature for 10 hours to fix the shape, and mature at room temperature for 72 hours to obtain a polyurethane foam material.

[0159] Example 6

[0160] The method described in Example 5 was followed, except that step (2) was as follows: 15 parts by weight of the prepolymer was weighed and added into a beaker, 0.15 parts by weight of fumed silica and 0.15 parts by weight of aerogel were added at a stirring speed of 600 rpm, and the mixture was stirred thoroughly to obtain a milky white premix.

[0161] Example 7

[0162] The method described in Example 1 was followed, except that step (1) was as follows: 100 parts by weight of polypropylene glycol (PPG1000) was weighed and added into a clean beaker, which was slowly heated to 105° C. under stirring, and dehydrated under vacuum negative pressure (-0.095 MPa) for 3 h. After cooling to 50° C., 51 parts by weight of isophorone diisocyanate was added, and the temperature was raised to 85° C. and kept warm for 4 h. The isocyanate content was tested to be 7.2%, thereby obtaining a prepolymer.

[0163] Example 8

[0164] The method described in Example 1 is implemented, except that the method for preparing the polyurethane foam comprises the following steps:

[0165] (1) 100 parts by weight of polytetrahydrofuran polyol (PTMG1000) were weighed and added into a clean three-necked flask, which was slowly heated to 105° C. under stirring, and dehydrated under vacuum negative pressure (−0.095 MPa) for 3 h. After the temperature was lowered to 50° C., 57 parts by weight of isophorone diisocyanate were added, and the temperature was raised to 85° C. and kept warm for 4 h. The isocyanate content was tested to be 8.0%, thereby obtaining a prepolymer.

[0166] (2) Weigh 15 parts by weight of the prepolymer into a beaker, add 0.1 parts by weight of fumed silica, 0.1 parts by weight of aerogel and 0.1 parts by weight of polymer microspheres at a stirring speed of 600 rpm, and stir thoroughly to obtain a milky white premix;

[0167] (3) Weigh 15 parts by weight of the premix, add 0.35 parts by weight of the polymer microsphere emulsion and 0.2 parts by weight of triethylenediamine at a stirring speed of 600 rpm, mix thoroughly and pour into a mold, foam at room temperature for 10 hours to set, and mature at room temperature for 72 hours to obtain a polyurethane foam material.

[0168] Example 9

[0169] The preparation method of the polymer microsphere emulsion and the polymer microsphere comprises the following steps:

[0170] Weigh 10 parts by weight of styrene and mix them evenly; add 2 parts by weight of acrylamide to 700 parts by weight of deionized water, stir and dissolve, place in a three-necked flask, heat to 80° C., add 0.1 parts by weight of potassium persulfate, dropwise add styrene into the three-necked flask, add 0.1 parts by weight of potassium persulfate after the reaction is carried out for 1 hour and 2 hours respectively, react for 4 hours, and obtain a uniform white emulsion, i.e., a polymer microsphere emulsion;

[0171] The polymer microsphere emulsion is dried in a freeze dryer to obtain powder, thereby obtaining polymer microspheres.

[0172] The preparation method of polyurethane foam material comprises the following steps:

[0173] (1) 100 parts by weight of polytetrahydrofuran polyol (PTMG1000) was weighed and added into a clean three-necked flask, which was slowly heated to 110° C. under stirring, and dehydrated under vacuum negative pressure (−0.095 MPa) for 2 h. After the temperature was lowered to 50° C., 51 parts by weight of isophorone diisocyanate was added, and the temperature was raised to 80° C. and kept warm for 4 h. The isocyanate content was tested to be 6.1%, thereby obtaining a prepolymer;

[0174] (2) Weigh 15 parts by weight of the prepolymer into a beaker, add 0.1 parts by weight of fumed silica, 0.2 parts by weight of aerogel and 0.2 parts by weight of polymer microspheres at a stirring speed of 600 rpm, and stir thoroughly to obtain a milky white premix;

[0175] (3) Weigh 15 parts by weight of the premix, add 0.3 parts by weight of the polymer microsphere emulsion and 0.2 parts by weight of stannous octoate at a stirring speed of 600 rpm, mix thoroughly and pour into a mold, foam at room temperature for 10 hours to set, and mature at room temperature for 72 hours to obtain a polyurethane foam material.

[0176] Example 10

[0177] The method described in Example 1 is used for implementation, except that the preparation process of the polymer microsphere emulsion and the polymer microsphere includes: weighing 10 parts by weight of styrene and mixing them evenly; adding 2 parts by weight of acrylic acid to 700 parts by weight of deionized water, stirring and dissolving, placing in a three-necked flask, heating to 85° C., adding 0.2 parts by weight of potassium persulfate, dropping styrene into the three-necked flask, adding 0.15 parts by weight of potassium persulfate after the reaction is carried out for 1 hour and 2 hours respectively, reacting for 4 hours, and obtaining a uniform white emulsion, namely, the polymer microsphere emulsion;

[0178] The polymer microsphere emulsion is dried in a freeze dryer to obtain powder, thereby obtaining polymer microspheres.

[0179] Comparative Example 1

[0180] Pure water is used as the foaming agent.

[0181] The specific steps include:

[0182] (1) Weigh 100 parts by weight of polytetrahydrofuran polyol into a clean three-necked flask, slowly heat it to 105° C. under stirring, dehydrate it under vacuum negative pressure (-0.095 MPa) for 3 h, cool it to 50° C., add 51 parts by weight of isophorone diisocyanate, heat it to 85° C., keep it warm for 4 h, and test the isocyanate content to be 6.1%, thereby obtaining a prepolymer;

[0183] (2) Weigh 15 parts by weight of the prepolymer into a beaker, add 0.1 parts by weight of fumed silica and 0.1 parts by weight of aerogel at a stirring speed of 600 rpm, and stir thoroughly to obtain a milky white premix;

[0184] (3) Weigh 15 parts by weight of the premix, add 0.3 parts by weight of pure water and 0.2 parts by weight of dibutyltin dilaurate at a stirring speed of 600 rpm, mix thoroughly and pour into a mold, foam at room temperature for 10 hours to set, and mature at room temperature for 72 hours to obtain a polyurethane foam material.

[0185] Comparative Example 2

[0186] The process was carried out as described in Example 1, except that no fillers (fumed silica, aerogel and polymer microspheres) were added.

[0187] The specific steps include:

[0188] (1) 100 parts by weight of polytetrahydrofuran polyol (PTMG1000) were weighed and added to a clean three-necked flask, which was slowly heated to 105° C. under stirring, and dehydrated under vacuum negative pressure (−0.095 MPa) for 3 h. After the temperature was lowered to 50° C., 51 parts by weight of isophorone diisocyanate were added, and the temperature was raised to 85° C. and kept warm for 4 h. The isocyanate content was tested to be 6.1%, thereby obtaining a prepolymer;

[0189] (2) Weigh 15 parts by weight of the prepolymer, add 0.3 parts by weight of the polymer microsphere emulsion and 0.2 parts by weight of dibutyltin dilaurate at a stirring speed of 600 rpm, mix thoroughly and pour into a mold, foam at room temperature for 10 hours to set, and mature at room temperature for 72 hours to obtain a polyurethane foam material.

[0190] Comparative Example 3

[0191] The fluorine-containing blowing agent trichlorofluoromethane is used for foaming.

[0192] The specific steps include:

[0193] (1) Weigh 100 parts by weight of polytetrahydrofuran polyol into a clean three-necked flask, slowly heat it to 105° C. under stirring, dehydrate it under vacuum negative pressure (-0.095 MPa) for 3 h, cool it to 50° C., add 51 parts by weight of isophorone diisocyanate, heat it to 85° C., keep it warm for 4 h, and test the isocyanate content to be 6.1%, thereby obtaining a prepolymer;

[0194] (2) Weigh 15 parts by weight of the prepolymer into a beaker, add 0.1 parts by weight of fumed silica and 0.1 parts by weight of aerogel at a stirring speed of 600 rpm, and stir thoroughly to obtain a milky white premix;

[0195] (3) Weigh 15 parts by weight of the premix, add 0.27 parts by weight of water, 0.03 parts by weight of a fluorine-containing foaming agent trichlorofluoromethane, and 0.2 parts by weight of dibutyltin dilaurate at a stirring speed of 600 rpm, mix thoroughly, pour into a mold, foam at room temperature for 10 hours to set, and mature at room temperature for 72 hours to obtain a polyurethane foam material.

[0196] Comparative Example 4

[0197] The method described in Example 1 was followed, except that no lipophilic polymerization monomer styrene was added when preparing the polymer microsphere emulsion.

[0198] Specifically, the process comprises the following steps: adding 11 parts by weight of acrylamide to 700 parts by weight of deionized water, stirring to dissolve, placing in a three-necked flask, heating to 80° C., adding 0.1 parts by weight of potassium persulfate, dropping acrylamide into the three-necked flask, adding 0.1 parts by weight of potassium persulfate after the reaction is carried out for 1 hour and 2 hours respectively, reacting for 4 hours, and obtaining a uniform white emulsion, i.e., a polymer microsphere emulsion;

[0199] The polymer microsphere emulsion was dried in a freeze dryer to obtain a white viscous polymer that was difficult to use as a filler.

[0200] Comparative Example 5

[0201] The method described in Example 1 was followed, except that no amphiphilic polymerizable monomer acrylamide was added when preparing the polymer microsphere emulsion.

[0202] The specific steps include:

[0203] The specific implementation steps are: weigh 10 parts by weight of styrene and mix them evenly; heat 700 parts by weight of deionized water to 80°C, add 0.1 parts by weight of potassium persulfate, drop styrene into a three-necked flask, add 0.1 parts by weight of potassium persulfate after the reaction is carried out for 1 hour and 2 hours respectively, react for 4 hours, and obtain a reaction liquid with oil-water two-phase separation, the upper layer is a viscous oily substance, which is difficult to use as a filler and a foaming agent.

[0204] Test Example 1

[0205] Figure 1 The pictures of the polymer emulsions prepared in Examples 1-4 are shown in ( Figure 1 a corresponds to Example 1, Figure 1 b corresponds to Example 2, Figure 1 c corresponds to Example 3, Figure 1 d corresponds to Example 4), Figure 2 is a graph showing the particle size test results of the polymer microspheres prepared in Examples 1-4; Figure 3 This is a picture of the polymer microspheres prepared in Example 2-3 ( Figure 3 a corresponds to Example 2, Figure 3 b corresponds to Example 3); Figure 4-7 They are scanning electron microscope images of the polymer microsphere emulsions prepared in Examples 1-4 after freeze-drying.

[0206] It can be seen from the above figures that the particle size distribution of the suspended microspheres in the polymer emulsions prepared in Examples 1-4 is uniform and the boundaries are clear.

[0207] Test Example 2

[0208] The test results of the density and thermal conductivity of the polyurethane foam materials prepared in Examples 1-10 and Comparative Examples 1-5 are shown in Table 1; the test results of the compressive strength of the polyurethane foam materials prepared in Examples 1-5 and Comparative Examples 1-2 are shown in Table 2. Figure 8 shown.

[0209] Table 1

[0210]

[0211]

[0212] From Table 1 and Figure 8 It can be seen that the polyurethane foam material prepared in the embodiment of the present invention has low density and thermal conductivity and good compression strength.

[0213] It can be seen from Example 5 and Comparative Example 1 that, compared with the case where the polymer emulsion is used as the foaming agent, the density and thermal conductivity of the polyurethane foam prepared by foaming with pure water become larger, the thermal insulation effect becomes worse, and the compression strength also becomes worse.

[0214] It can be seen from Examples 1 / 5 / 6 and Comparative Example 2 that the density and thermal conductivity of the polyurethane foam prepared without adding fillers are increased, and the thermal insulation effect is poor.

[0215] It can be seen from Example 5 and Comparative Example 3 that the polymer microsphere emulsion (90 wt % of which is water and 10 wt % of which is polymer microsphere particles) as a foaming agent has a lower density and thermal conductivity coefficient and a better thermal insulation effect than the conventional fluorine-containing foaming agent with the same amount.

[0216] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A polyurethane foam material, characterized in that: The polyurethane foam material is made of a raw material composition containing polyol, isocyanate, catalyst, polymer microsphere emulsion and filler; Wherein, the filler contains one or more of aerogel, fumed silica and polymer microspheres; The polymer microsphere emulsion is prepared by soap-free emulsion polymerization. Its preparation raw materials contain lipophilic polymerization monomers and amphiphilic polymerization monomers. The polymer microspheres are prepared by drying the polymer microsphere emulsion.

2. The polyurethane foam material according to claim 1, characterized in that The polymer microsphere emulsion is prepared according to the following steps: The amphiphilic polymerizable monomer and water are mixed and stirred, and then a water-soluble initiator and a lipophilic polymerizable monomer are added to react.

3. The polyurethane foam material according to claim 2, characterized in that: The weight ratio of the lipophilic polymerizable monomer, the amphiphilic polymerizable monomer and the water-soluble initiator is 10:1-6:0.2-1; Preferably, the reaction conditions include: temperature of 70-90°C and time of 3-5h; Preferably, the water-soluble initiator is potassium persulfate and / or ammonium persulfate.

4. The polyurethane foam material according to any one of claims 1 to 3, characterized in that: The lipophilic polymerizable monomer is selected from one or more of styrene, 4-methylstyrene, 4-tert-butylstyrene, methyl acrylate, methyl methacrylate, butyl acrylate, isooctyl acrylate and isooctyl methacrylate; Preferably, the amphiphilic polymerizable monomer is acrylic acid and / or acrylamide.

5. The polyurethane foam material according to any one of claims 1 to 4, characterized in that: The density of the aerogel is 30-50 kg / m 3 , porosity>90%, specific surface area 500~650m 2 / g; Preferably, the density of the fumed silica is 55 to 60 kg / m 3 , specific surface area 380~400m 2 / g.

6. The polyurethane foam material according to any one of claims 1 to 4, characterized in that: The polyol is polypropylene glycol and / or polytetrahydrofuran polyol; Preferably, the isocyanate is one or more of isophorone diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate; Preferably, the catalyst is selected from one or more of triethylenediamine, bis(dimethylaminoethyl) ether, stannous octoate, tin naphthenate and dibutyltin dilaurate.

7. The polyurethane foam material according to any one of claims 1 to 6, characterized in that: The weight ratio of the polyol to the isocyanate is 100:45-70.

8. A method for preparing a polyurethane foam material, characterized in that: The method comprises the following steps: (1) heating and dehydrating the polyol, and then mixing and reacting the polyol with isocyanate to obtain a prepolymer having an isocyanate content of 5 to 10%; (2) mixing the prepolymer and the filler to obtain a premix; (3) mixing the premix with the polymer microsphere emulsion and the catalyst, and then foaming and ripening; The filler contains one or more of aerogel, fumed silica and polymer microspheres, and the polymer microspheres are obtained by drying the polymer microsphere emulsion.

9. The method according to claim 8, characterized in that In step (1), the heating dehydration process comprises: heating the polyol to 100-110° C. and dehydrating for 2-3 hours under a vacuum degree of -0.07-0.1 MPa; Preferably, in step (1), the reaction conditions include: temperature of 75 to 95° C., time of 3 to 4 h; Preferably, in step (1), the weight ratio of the polyol to the isocyanate is 100:45-70.

10. The method according to claim 8, characterized in that In step (2), the weight ratio of the prepolymer to the filler is 15: 0.1～1。 11. The method according to claim 8, characterized in that In step (3), the weight ratio of the premix, the polymer microsphere emulsion and the catalyst is 15: 0.1～1：0.1～0.5； Preferably, in step (3), the foaming conditions include: temperature of 20 to 30° C., time of 5 to 15 h; Preferably, in step (3), the aging conditions include: a temperature of 20 to 30° C. and a time of 48 to 100 hours.

12. The method according to any one of claims 8 to 11, characterized in that: The method further comprises preparing the polymer microsphere emulsion according to the following steps: mixing and stirring the amphiphilic polymer monomer and water, and then adding a water-soluble initiator and a lipophilic polymer monomer to react; Preferably, the weight ratio of the lipophilic polymerizable monomer, the amphiphilic polymerizable monomer and the water-soluble initiator is 10:1-6:0.2-1; Preferably, when preparing the polymer microsphere emulsion, the reaction conditions include: temperature of 70 to 90° C., time of 3 to 5 h; Preferably, the water-soluble initiator is potassium persulfate and / or ammonium persulfate; Preferably, the lipophilic polymerizable monomer is selected from one or more of styrene, 4-methylstyrene, 4-tert-butylstyrene, methyl acrylate, methyl methacrylate, butyl acrylate, isooctyl acrylate and isooctyl methacrylate; Preferably, the amphiphilic polymerizable monomer is acrylic acid and / or acrylamide.

13. The method according to any one of claims 8 to 12, characterized in that: The polyol is polypropylene glycol and / or polytetrahydrofuran polyol; Preferably, the isocyanate is one or more of isophorone diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate; Preferably, the catalyst is selected from one or more of triethylenediamine, bis(dimethylaminoethyl) ether, stannous octoate, tin naphthenate and dibutyltin dilaurate.

14. The polyurethane foam material prepared by the method according to any one of claims 8 to 13.

15. Use of the polyurethane foam material according to any one of claims 1 to 7 and 14 in the preparation of thermal insulation products.

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