A kind of breathable polyurethane foam sponge and preparation method thereof

Abstract

The present invention provides a breathable polyurethane foam sponge and a preparation method thereof, and relates to the technical field of foam sponges, and is made of the following raw materials by weight: 60-70 parts of functional polyurethane, 5-8 parts of plant fiber powder, 0.8-1.5 parts of coupling agent, 4-6 parts of 4,4'-diacyl chloride diphenyl ether, 1-2 parts of pentafluorobenzoyl chloride, 1-3 parts of furanoyl chloride, 0.8-1.2 parts of catalyst A, and 3-5 parts of foaming agent; the functional polyurethane includes a structural unit introduced by the following monomers: polytetrahydrofuran ether diol, dimethyl biphenyl diisocyanate, bis (3-aminophenyl) 3,5-bis (trifluoromethyl) phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone. The sponge has good mechanical properties, good air permeability, sufficient flame retardancy and moisture-heat aging resistance, and strong compression permanent deformation resistance.

Description

Technical Field

[0001] The invention relates to the technical field of foamed sponge materials, and in particular to a breathable polyurethane foamed sponge and a preparation method thereof. Background Art

[0002] Polyurethane material is a polymer material containing carbamate groups in the main chain of the macromolecule. The polyurethane foam sponge prepared after the polyurethane material is foamed has good resilience, mechanical properties and corrosion resistance, etc., and has been widely used in household goods, automobiles, footwear, medical equipment and other fields. With the further expansion of its application scope, the performance requirements for polyurethane foam sponge are becoming more and more stringent. The ideal polyurethane foam sponge should have excellent air permeability, flame retardancy, mechanical properties and resilience.

[0003] Traditional polyurethane foam sponges have a large number of pores, a high specific surface area, and a large contact area with the air, so their flame retardancy is often poor. In the event of a fire, they are easily ignited, producing a large amount of toxic gases and releasing a large amount of heat. In addition, due to the poor opening performance of this type of foam sponge, their air permeability is poor. In addition, the polyurethane foam sponges on the market have more or less technical defects such as limited mechanical properties, insufficient stability, easy deformation, and short service life.

[0004] For example, the Chinese invention patent with the authorization announcement number CN114621576B discloses a yellowing-resistant polyurethane sponge and a preparation method thereof, wherein the yellowing-resistant polyurethane sponge comprises: a polyurethane foam; a heat-insulating layer embedded in the polyurethane foam, and phase-change particles are arranged in the heat-insulating layer. The yellowing-resistant polyurethane sponge and the preparation method thereof described in the invention have the advantages of good yellowing-resistant effect, long service life, simple and easy-to-obtain raw materials, simple and stable preparation process, and are conducive to large-scale industrial production and application. However, its flame retardancy and air permeability are insufficient.

[0005] It can be seen that it is particularly important to develop a breathable polyurethane foam sponge with good mechanical properties, good air permeability, sufficient flame retardancy and resistance to moisture and heat aging, and strong resistance to compression permanent deformation and a preparation method thereof. Summary of the invention

[0006] In view of the above problems, the object of the present invention is to provide a breathable polyurethane foam sponge with good mechanical properties, good air permeability, sufficient flame retardancy and resistance to moisture and heat aging, and strong resistance to permanent compression deformation, and a preparation method thereof.

[0007] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present invention is: a breathable polyurethane foam sponge is made of the following raw materials in parts by weight: 60-70 parts of functional polyurethane, 5-8 parts of plant fiber powder, 0.8-1.5 parts of coupling agent, 4-6 parts of 4,4'-diacyl chloride diphenyl ether, 1-2 parts of pentafluorobenzoyl chloride, 1-3 parts of furanyl chloride, 0.8-1.2 parts of catalyst A, and 3-5 parts of foaming agent; the functional polyurethane includes structural units introduced by the following monomers: polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, and 2,7-dihydroxy-9-fluorenone.

[0008] Preferably, the preparation method of the functional polyurethane comprises the following steps: adding polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone and catalyst B to a high boiling point solvent, stirring and reacting at 70-90° C. for 3-5 hours in an inert gas atmosphere, then heating to 92-97° C. and continuing to stir and react for 6-12 hours, then precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and then removing the residual solvent by rotary evaporation to obtain the functional polyurethane.

[0009] Preferably, the molar ratio of the polytetramethylene oxide diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone, catalyst B, and high boiling point solvent is 0.5:1:0.2:0.3:(0.8-1.2):(6-10).

[0010] Preferably, the polytetramethylene ether glycol is polytetramethylene ether glycol PTMG1000.

[0011] Preferably, the catalyst B is at least one of dibutyltin dilaurate and stannous octoate; the high boiling point solvent is dimethyl sulfoxide; and the inert gas is any one of nitrogen, helium, neon and argon.

[0012] Preferably, the plant fiber powder is at least one of wood powder, bamboo powder and bran powder.

[0013] Preferably, the particle size of the plant fiber powder is 300-600 mesh.

[0014] Preferably, the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570.

[0015] Preferably, the catalyst A is a mixture of anhydrous aluminum chloride and anhydrous zinc chloride in a mass ratio of 1:(3-5).

[0016] Preferably, the foaming agent is a mixture of foaming agent TSH and N,N'-dinitroso-N,N'-dimethylterephthalamide in a mass ratio of 1:(1-2).

[0017] Another object of the present invention is to provide a method for preparing the breathable polyurethane foam sponge, comprising the following steps:

[0018] Step S1, after mixing the raw materials uniformly by weight to obtain a mixed material, the mixed material is uniformly dispersed in an organic solvent to obtain a dispersion;

[0019] Step S2: pour the dispersion into a mold, foam and dry to obtain a breathable polyurethane foam sponge.

[0020] Preferably, the mass ratio of the mixed material to the organic solvent is 1:(3-5); the organic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0021] Preferably, the foaming temperature is 112-116° C., and the heat preservation time is 18-26 minutes; the drying temperature is 126-136° C., and the drying time is 1-3 hours.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The preparation method of the breathable polyurethane foam sponge disclosed in the present invention is simple, easy to operate, can effectively improve production efficiency, is conducive to saving labor costs, is suitable for large-scale production, and has strong practicality.

[0024] (2) The breathable polyurethane foam sponge disclosed in the present invention is made of the following raw materials in parts by weight: 60-70 parts of functional polyurethane, 5-8 parts of plant fiber powder, 0.8-1.5 parts of coupling agent, 4-6 parts of 4,4'-diacyl chloride diphenyl ether, 1-2 parts of pentafluorobenzoyl chloride, 1-3 parts of furanoyl chloride, 0.8-1.2 parts of catalyst A, and 3-5 parts of foaming agent; the functional polyurethane includes structural units introduced by the following monomers: polytetrahydrofuran ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, and 2,7-dihydroxy-9-fluorenone. Through the mutual coordination and joint action of the raw materials, the prepared breathable polyurethane foam sponge has good mechanical properties, good air permeability, sufficient flame retardancy and moisture-heat aging resistance, and strong resistance to compression permanent deformation.

[0025] (3) The breathable polyurethane foam sponge disclosed in the present invention comprises structural units introduced by the following monomers: polytetrahydrofuran ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone; the raw materials with acyl chloride groups can react with the benzene ring on the functional polyurethane to form an interpenetrating network structure, and furan and pentafluorobenzene structures are introduced at the same time. These structures, under the multiple effects of electronic effect, steric effect and conjugation effect, make the manufactured product have better mechanical properties, better air permeability, better flame retardancy and resistance to wet and hot aging, and stronger resistance to compression permanent deformation. The addition of plant fiber powder can not only improve the mechanical properties, but also cooperate with other raw materials to improve air permeability.

[0026] (4) The breathable polyurethane foam sponge disclosed in the present invention has a uniform pore size and a high open porosity through the reasonable selection of raw material types, dosage ratios and process parameters, so that the product has good air permeability and mechanical properties, strong resistance to permanent compression deformation and a long service life. DETAILED DESCRIPTION

[0027] In order to enable those skilled in the art to better understand the technical solution of the present invention, the product of the present invention is further described in detail below in conjunction with embodiments.

[0028] Example 1

[0029] A breathable polyurethane foam sponge is prepared from the following raw materials in parts by weight: 60 parts of functional polyurethane, 5 parts of plant fiber powder, 0.8 parts of coupling agent, 4 parts of 4,4'-diacyl chloride diphenyl ether, 1 part of pentafluorobenzoyl chloride, 1 part of furanyl chloride, 0.8 parts of catalyst A, and 3 parts of foaming agent; the functional polyurethane comprises structural units introduced by the following monomers: polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, and 2,7-dihydroxy-9-fluorenone.

[0030] The preparation method of the functional polyurethane comprises the following steps: adding polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, 2,7-dihydroxy-9-fluorenone and catalyst B to a high boiling point solvent, stirring and reacting for 3 hours at 70°C in an inert gas atmosphere, then heating to 92°C and continuing stirring and reacting for 6 hours, then precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and then rotary evaporating to remove the residual solvent to obtain the functional polyurethane; the polytetramethylene glycol The molar ratio of furan ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone, catalyst B, and high boiling point solvent is 0.5:1:0.2:0.3:0.8:6; the polytetrahydrofuran ether diol is polytetrahydrofuran ether diol PTMG1000; the catalyst B is dibutyltin dilaurate; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen; the M of the functional polyurethane is measured by GPC test. n =15173 g / mol, M W / M n =1.352; through elemental analysis and weight change calculation, the molar ratio of the structural units introduced by polytetramethylene glycol, dimethylbiphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide and 2,7-dihydroxy-9-fluorenone in the functional polyurethane is the same as the theoretical value.

[0031] The plant fiber powder is wood powder; the particle size of the plant fiber powder is 300 meshes; the coupling agent is silane coupling agent KH550; the catalyst A is a mixture of anhydrous aluminum chloride and anhydrous zinc chloride in a mass ratio of 1:3; the foaming agent is a mixture of foaming agent TSH and N,N'-dinitroso-N,N'-dimethylterephthalamide in a mass ratio of 1:1.

[0032] A method for preparing the breathable polyurethane foam sponge comprises the following steps:

[0033] Step S1, after mixing the raw materials uniformly by weight, obtaining a mixed material, and dispersing the mixed material uniformly in an organic solvent to obtain a dispersion; the mass ratio of the mixed material to the organic solvent is 1:3; and the organic solvent is N,N-dimethylformamide;

[0034] Step S2, pouring the dispersion into a mold, foaming and drying to obtain a breathable polyurethane foam sponge; the foaming temperature is 112° C., and the temperature is kept warm for 18 minutes; the drying temperature is 126° C., and the drying time is 1 hour.

[0035] Example 2

[0036] A breathable polyurethane foam sponge is prepared from the following raw materials in parts by weight: 63 parts of functional polyurethane, 6 parts of plant fiber powder, 1 part of coupling agent, 4.5 parts of 4,4'-diacyl chloride diphenyl ether, 1.2 parts of pentafluorobenzoyl chloride, 1.5 parts of furanoyl chloride, 0.9 parts of catalyst A, and 3.5 parts of foaming agent; the functional polyurethane comprises structural units introduced by the following monomers: polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, and 2,7-dihydroxy-9-fluorenone.

[0037] The preparation method of the functional polyurethane comprises the following steps: adding polytetrahydrofuran ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, 2,7-dihydroxy-9-fluorenone and catalyst B to a high boiling point solvent, stirring and reacting for 3.5 hours at 75°C in an inert gas atmosphere, then heating to 93°C and continuing stirring and reacting for 8 hours, then precipitating in water, washing the precipitated polymer with ethanol for 4 times, and then rotary evaporating to remove the residual solvent to obtain to functional polyurethane; the molar ratio of the polytetramethylene ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone, catalyst B, and high boiling point solvent is 0.5:1:0.2:0.3:0.9:7; the polytetramethylene ether diol is polytetramethylene ether diol PTMG1000; the catalyst B is stannous octoate; the high boiling point solvent is dimethyl sulfoxide; and the inert gas is helium.

[0038] The plant fiber powder is bamboo powder; the particle size of the plant fiber powder is 400 mesh; the coupling agent is silane coupling agent KH560; the catalyst A is a mixture of anhydrous aluminum chloride and anhydrous zinc chloride in a mass ratio of 1:3.5; the foaming agent is a mixture of foaming agent TSH and N,N'-dinitroso-N,N'-dimethylterephthalamide in a mass ratio of 1:1.2.

[0039] A method for preparing the breathable polyurethane foam sponge comprises the following steps:

[0040] Step S1, after mixing the raw materials uniformly by weight, obtaining a mixed material, and dispersing the mixed material uniformly in an organic solvent to obtain a dispersion; the mass ratio of the mixed material to the organic solvent is 1:3.5; and the organic solvent is N,N-dimethylacetamide;

[0041] Step S2, pouring the dispersion into a mold, foaming and drying to obtain a breathable polyurethane foam sponge; the foaming temperature is 113°C, and the temperature is kept for 20 minutes; the drying temperature is 129°C, and the time is 1.5 hours.

[0042] Example 3

[0043] A breathable polyurethane foam sponge is prepared from the following raw materials in parts by weight: 65 parts of functional polyurethane, 6.5 parts of plant fiber powder, 1.2 parts of coupling agent, 5 parts of 4,4'-diacyl chloride diphenyl ether, 1.5 parts of pentafluorobenzoyl chloride, 2 parts of furanyl chloride, 1 part of catalyst A, and 4 parts of foaming agent; the functional polyurethane comprises structural units introduced by the following monomers: polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, and 2,7-dihydroxy-9-fluorenone.

[0044] The preparation method of the functional polyurethane comprises the following steps: adding polytetrahydrofuran ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, 2,7-dihydroxy-9-fluorenone and catalyst B to a high boiling point solvent, stirring and reacting at 80°C for 4 hours in an inert gas atmosphere, then heating to 95°C and continuing stirring and reacting for 9 hours, then precipitating in water, washing the precipitated polymer with ethanol for 5 times, and then rotary evaporating to remove the residual solvent to obtain the functional polyurethane. Polyurethane; the molar ratio of the polytetramethylene ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone, catalyst B, and high boiling point solvent is 0.5:1:0.2:0.3:1:8; the polytetramethylene ether diol is polytetramethylene ether diol PTMG1000; the catalyst B is dibutyltin dilaurate; the high boiling point solvent is dimethyl sulfoxide; and the inert gas is neon.

[0045] The plant fiber powder is bran powder; the particle size of the plant fiber powder is 450 mesh; the coupling agent is silane coupling agent KH570; the catalyst A is a mixture of anhydrous aluminum chloride and anhydrous zinc chloride in a mass ratio of 1:4; the foaming agent is a mixture of foaming agent TSH and N,N'-dinitroso-N,N'-dimethylterephthalamide in a mass ratio of 1:1.5.

[0046] A method for preparing the breathable polyurethane foam sponge comprises the following steps:

[0047] Step S1, after mixing the raw materials uniformly by weight, obtaining a mixed material, and dispersing the mixed material uniformly in an organic solvent to obtain a dispersion; the mass ratio of the mixed material to the organic solvent is 1:4; and the organic solvent is N-methylpyrrolidone;

[0048] Step S2, pouring the dispersion into a mold, foaming and drying to obtain a breathable polyurethane foam sponge; the foaming temperature is 114° C., and the temperature is kept warm for 22 minutes; the drying temperature is 130° C., and the drying time is 2 hours.

[0049] Example 4

[0050] A breathable polyurethane foam sponge is prepared from the following raw materials in parts by weight: 68 parts of functional polyurethane, 7.5 parts of plant fiber powder, 1.3 parts of coupling agent, 5.5 parts of 4,4'-diacyl chloride diphenyl ether, 1.8 parts of pentafluorobenzoyl chloride, 2.5 parts of furanoyl chloride, 1.1 parts of catalyst A, and 4.5 parts of foaming agent; the functional polyurethane comprises structural units introduced by the following monomers: polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, and 2,7-dihydroxy-9-fluorenone.

[0051] The preparation method of the functional polyurethane comprises the following steps: adding polytetrahydrofuran ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, 2,7-dihydroxy-9-fluorenone and catalyst B to a high boiling point solvent, stirring and reacting for 4.5 hours at 85°C in an inert gas atmosphere, then heating to 96°C and continuing stirring and reacting for 11 hours, then precipitating in water, washing the precipitated polymer with ethanol for 6 times, and then rotary evaporating to remove the residual solvent to obtain the functional polyurethane; the polytetrahydrofuran ether diol The molar ratio of polytetrahydrofuran ether diol, dimethylbiphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone, catalyst B, and high boiling point solvent is 0.5:1:0.2:0.3:1.1:9.5; the polytetrahydrofuran ether diol is polytetrahydrofuran ether diol PTMG1000; the catalyst B is a mixture of dibutyltin dilaurate and stannous octoate in a mass ratio of 1:3; the high boiling point solvent is dimethyl sulfoxide; and the inert gas is argon.

[0052] The plant fiber powder is a mixture of wood powder, bamboo powder and bran powder in a mass ratio of 1:1:2; the particle size of the plant fiber powder is 550 mesh; the coupling agent is a mixture of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH570 in a mass ratio of 1:3:5; the catalyst A is a mixture of anhydrous aluminum chloride and anhydrous zinc chloride in a mass ratio of 1:4.5; the foaming agent is a mixture of foaming agent TSH and N,N'-dinitroso-N,N'-dimethylterephthalamide in a mass ratio of 1:1.8.

[0053] A method for preparing the breathable polyurethane foam sponge comprises the following steps:

[0054] Step S1, after mixing the raw materials uniformly by weight, obtaining a mixed material, and dispersing the mixed material uniformly in an organic solvent to obtain a dispersion; the mass ratio of the mixed material to the organic solvent is 1:4.5; the organic solvent is a mixture of N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone in a mass ratio of 1:3:5;

[0055] Step S2, pouring the dispersion into a mold, foaming and drying to obtain a breathable polyurethane foam sponge; the foaming temperature is 115°C, and the temperature is kept for 25 minutes; the drying temperature is 135°C, and the time is 2.5 hours.

[0056] Example 5

[0057] A breathable polyurethane foam sponge is prepared from the following raw materials in parts by weight: 70 parts of functional polyurethane, 8 parts of plant fiber powder, 1.5 parts of coupling agent, 6 parts of 4,4'-diacyl chloride diphenyl ether, 2 parts of pentafluorobenzoyl chloride, 3 parts of furancarbonyl chloride, 1.2 parts of catalyst A, and 5 parts of foaming agent; the functional polyurethane comprises structural units introduced by the following monomers: polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, and 2,7-dihydroxy-9-fluorenone.

[0058] The preparation method of the functional polyurethane comprises the following steps: adding polytetrahydrofuran ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, 2,7-dihydroxy-9-fluorenone and catalyst B to a high boiling point solvent, stirring and reacting for 5 hours at 90° C. in an inert gas atmosphere, then heating to 97° C. and continuing stirring and reacting for 12 hours, then precipitating in water, washing the precipitated polymer with ethanol for 6 times, and then rotary evaporating to remove the residual solvent to obtain the functional polyurethane. The invention relates to a polytetramethylene oxide (PTMG)-containing compound. The polytetramethylene oxide (PTMG-containing compound) is prepared from polytetramethylene oxide (PTMG-containing compound). The polytetramethylene oxide (PTMG-containing compound) is prepared from polytetramethylene oxide (PTMG-containing compound). The invention relates to a polytetramethylene oxide (PTMG-containing compound). The invention relates to a polytetramethylene oxide (PTMG-containing compound). The invention relates to a polytetramethylene oxide (PTMG-containing compound).

[0059] The plant fiber powder is wood powder; the particle size of the plant fiber powder is 600 mesh; the coupling agent is silane coupling agent KH550; the catalyst A is a mixture of anhydrous aluminum chloride and anhydrous zinc chloride in a mass ratio of 1:5; the foaming agent is a mixture of foaming agent TSH and N,N'-dinitroso-N,N'-dimethylterephthalamide in a mass ratio of 1:2.

[0060] A method for preparing the breathable polyurethane foam sponge comprises the following steps:

[0061] Step S1, after mixing the raw materials uniformly by weight, obtaining a mixed material, and dispersing the mixed material uniformly in an organic solvent to obtain a dispersion; the mass ratio of the mixed material to the organic solvent is 1:5; and the organic solvent is N,N-dimethylformamide;

[0062] Step S2, pouring the dispersion into a mold, foaming and drying to obtain a breathable polyurethane foam sponge; the foaming temperature is 116°C and the temperature is kept for 26 minutes; the drying temperature is 136°C and the drying time is 3 hours.

[0063] Comparative Example 1

[0064] A breathable polyurethane foam sponge is substantially the same as Example 1, except that pentafluorobenzoyl chloride is not added and polytetramethylene glycol is used instead of 2,7-dihydroxy-9-fluorenone.

[0065] Comparative Example 2

[0066] A breathable polyurethane foam sponge is substantially the same as Example 1, except that furanoyl chloride is not added and polytetramethylene glycol is used instead of bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide.

[0067] In order to further illustrate the unexpected positive technical effects achieved by the products of each embodiment of the present invention, relevant performance tests were performed on the breathable polyurethane foam sponges prepared in each example. The test results are shown in Table 1. The test methods are as follows: the tensile strength is tested with reference to the method of standard ISO 1798-2008; the compression permanent deformation is tested with reference to the method of standard ISO 1856-2007; the conditions for wet heat aging are: temperature 80°C, humidity 95%, aging 120h; the oxygen index is tested with reference to GB / T 10707-2008; and the open porosity is tested using a polyurethane open and closed porosity tester.

[0068] As can be seen from Table 1, the breathable polyurethane foam sponge disclosed in the embodiment of the present invention has better mechanical properties, resistance to permanent deformation and resistance to moist and hot aging than the comparative example product, and has better flame retardancy and air permeability. The combined use of furanoyl chloride, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, pentafluorobenzoyl chloride and 2,7-dihydroxy-9-fluorenone is beneficial to improving the above properties.

[0069] Table 1

[0070]

[0071] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any ordinary technician in the industry can smoothly implement the present invention as described above. However, any technician familiar with the profession can make some changes, modifications and evolutions of the technical content disclosed above without departing from the scope of the technical solution of the present invention, which are all equivalent embodiments of the present invention. At the same time, any changes, modifications and evolutions of any equivalent changes made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the technical solution of the present invention.

Claims

1. A breathable polyurethane foam sponge, characterized in that: The functional polyurethane is prepared from the following raw materials in parts by weight: 60-70 parts of functional polyurethane, 5-8 parts of plant fiber powder, 0.8-1.5 parts of coupling agent, 4-6 parts of 4,4'-diacyl chloride diphenyl ether, 1-2 parts of pentafluorobenzoyl chloride, 1-3 parts of furanyl chloride, 0.8-1.2 parts of catalyst A, and 3-5 parts of foaming agent; the functional polyurethane comprises structural units introduced by the following monomers: polytetrahydrofuran ether diol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl) 3,5-bis(trifluoromethyl)phenyl phosphine oxide, and 2,7-dihydroxy-9-fluorenone; The preparation method of the functional polyurethane comprises the following steps: adding polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone and catalyst B to a high boiling point solvent, stirring and reacting for 3-5 hours at 70-90° C. in an inert gas atmosphere, then heating to 92-97° C. and continuing stirring and reacting for 6-12 hours, then precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and then removing the residual solvent by rotary evaporation to obtain the functional polyurethane; the molar ratio of the polytetramethylene glycol, dimethyl biphenyl diisocyanate, bis(3-aminophenyl)3,5-bis(trifluoromethyl)phenylphosphine oxide, 2,7-dihydroxy-9-fluorenone, catalyst B and high boiling point solvent is 0.5:1:0.2:0.3:(0.8-1.2):(6-10).

2. The breathable polyurethane foam sponge according to claim 1, characterized in that: The polytetramethylene ether glycol is polytetramethylene ether glycol PTMG1000.

3. The breathable polyurethane foam sponge according to claim 1, characterized in that: The catalyst B is at least one of dibutyltin dilaurate and stannous octoate; the high boiling point solvent is dimethyl sulfoxide; and the inert gas is any one of nitrogen, helium, neon and argon.

4. The breathable polyurethane foam sponge according to claim 1, characterized in that: The plant fiber powder is at least one of wood powder, bamboo powder and bran powder; the particle size of the plant fiber powder is 300-600 meshes.

5. The breathable polyurethane foam sponge according to claim 1, characterized in that: The coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH570.

6. The breathable polyurethane foam sponge according to claim 1, characterized in that: The catalyst A is a mixture of anhydrous aluminum chloride and anhydrous zinc chloride in a mass ratio of 1:(3-5); the foaming agent is a mixture of foaming agent TSH and N,N'-dinitroso-N,N'-dimethylterephthalamide in a mass ratio of 1:(1-2).

7. A method for preparing the breathable polyurethane foam sponge according to any one of claims 1 to 6, characterized in that: The steps include: Step S1, after mixing the raw materials uniformly by weight to obtain a mixed material, the mixed material is uniformly dispersed in an organic solvent to obtain a dispersion; Step S2: pour the dispersion into a mold, foam and dry to obtain a breathable polyurethane foam sponge.

8. The method for preparing the breathable polyurethane foam sponge according to claim 7, characterized in that: The mass ratio of the mixed material to the organic solvent is 1:(3-5); the organic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; the foaming temperature is 112-116° C., and the heat preservation time is 18-26 minutes; the drying temperature is 126-136° C., and the drying time is 1-3 hours.

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