Polyurethane foam material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of polyurethane foam, and particularly relates to a polyurethane foam material as well as a preparation method and application thereof. The polyurethane foam material is a product obtained by reaction of a polyether polyol composition A and a modified isocyanate prepolymer B, the polyether polyol composition A comprises a polyether polyol mixture and a combined auxiliary agent; the polyether polyol mixture includes: (a) a polyether polyol having a hydroxyl value of 18 to 80 mgKOH / g; the ethylene oxide content is 2-18 wt%; (b) a product obtained by copolymerization graft modification of polyether polyol, styrene and acrylonitrile, wherein the hydroxyl value is 18-80 mgKOH / g; the ethylene oxide content is 2-18 wt%; and (c) a polyether polyol having a molecular weight of 300 to 1000, a hydroxyl value of 160 to 350 mgKOH / g, and an ethylene oxide content of 0 to 5 wt%. The polyurethane foam material disclosed by the invention has the advantages of slow resilience and air permeability.

Description

Technical Field

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

[0002] The mainstream insole material in this field is EVA (ethylene-vinyl acetate copolymer), but it has problems such as poor compression deformation and insufficient air permeability. Poor compression deformation shortens the life of the insole, and the insole cannot be deformed after long-term wearing; insufficient air permeability can cause the feet to be blocked and sweat cannot be eliminated in time.

[0003] At present, PU materials have been used in insoles to replace part of EVA. The advantage of PU materials is excellent compression permanent deformation. High-rebound PU can also be breathable, but high-rebound materials have high support and exert certain pressure on the soles of the feet.

[0004] Slow-rebound materials have unique temperature-sensitive properties. They become soft when heated and hard when cooled. When exposed to human body temperature, the particles on the surface soften. As the body's weight softens, the particles evenly distribute the pressure area, eliminating pressure points and ensuring that the blood in the body will not be compressed under any circumstances. The pressure-relieving property avoids pain and discomfort caused by rebound pressure or human gravity.

[0005] The prior art discloses some technical solutions for slow-rebound insole materials. For example, patent document CN 106565932A discloses a highly plastic slow-rebound polyurethane foam shoe material and a preparation method. The material has good support performance, fits well with the curve of the sole of the foot, has excellent resistance to compression deformation, and can still maintain a good initial shape after long-term wear and use, but the material is not breathable. Patent document CN105237719A discloses a method for preparing a polyurethane insole. The resulting product has good comfort and greatly protects the safety of the athlete's soles; but the foam does not have the characteristics of slow rebound elasticity.

[0006] The problem with slow-rebound materials is that they are not breathable due to their high cross-linking density, which makes them easy to cause foot-suffocation, just like EVA. In view of this, how to further improve slow-rebound materials to make them comfortable and breathable is a direction worth continuing to study. Summary of the invention

[0007] The purpose of the present invention is to provide a polyurethane foam material and a preparation method and application thereof, in view of the problem of poor air permeability of slow-rebound materials in the prior art; by improving the formula of the main reaction components, a polyether polyol composition and a modified isocyanate prepolymer, the obtained polyurethane foam material has the advantages of slow rebound and air permeability.

[0008] In order to achieve the above object, the present invention provides the following technical solutions:

[0009] In a first aspect, a polyurethane foam material is provided, which is a product obtained by reacting a polyether polyol composition A and a modified isocyanate prepolymer B;

[0010] The polyether polyol composition A comprises: a polyether polyol mixture and a combination auxiliary agent; wherein,

[0011] The polyether polyol mixture comprises the following components:

[0012] (a) a polyether polyol having an average functionality of 2 to 4 (e.g., 2, 3, 4), a number average molecular weight of 2000 to 8000 (e.g., 2100, 2400, 2500, 3000, 3200, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500), and a hydroxyl value of 18 mgKOH / g to 80 mgKOH / g (e.g., 20 mgKOH / g , 25mgKOH / g, 30mgKOH / g, 35mgKOH / g, 40mgKOH / g, 45mgKOH / g, 50mgKOH / g, 55mgKOH / g, 60mgKOH / g, 65mgKOH / g, 70mgKOH / g, 75mgKOH / g); the ethylene oxide content is 2wt% to 18wt% (for example, 4wt%, 5wt%, 10wt%, 15wt%);

[0013] (b) polyether polyol, a product obtained by copolymerization and grafting modification of styrene and acrylonitrile, having a solid content of 20 wt % to 45 wt % (e.g., 25 wt %, 30 wt %, 35 wt %, 40 wt %), an average functionality of 2 to 4 (e.g., 2, 3, 4), a number average molecular weight of 2000 to 5000 (e.g., 2100, 2400, 2500, 3000, 3200, 3500, 4000, 4500, 4800), and a hydroxyl value of 18 mgKOH / g to 80 mgKOH / g. gKOH / g (e.g., 20 mgKOH / g, 25 mgKOH / g, 30 mgKOH / g, 35 mgKOH / g, 40 mgKOH / g, 45 mgKOH / g, 50 mgKOH / g, 55 mgKOH / g, 60 mgKOH / g, 65 mgKOH / g, 70 mgKOH / g, 75 mgKOH / g); ethylene oxide content of 2 wt % to 18 wt % (e.g., 4 wt %, 5 wt %, 10 wt %, 15 wt %);

[0014] (c) a polyether polyol having an average functionality of 2 to 4 (e.g., 2, 3, 4), a number average molecular weight of 300 to 1000 (e.g., 320, 340, 350, 400, 500, 600, 700, 800, 900, 950), a hydroxyl value of 160 to 350 mgKOH / g (e.g., 165 mgKOH / g, 180 mgKOH / g, 200 mgKOH / g, 250 mgKOH / g, 300 mgKOH / g, 340 mgKOH / g), and an ethylene oxide content of 0 to 5 wt % (e.g., 0.1 wt %, 0.5 wt %, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 4.5 wt %);

[0015] The combination of auxiliary agents at least includes a cell-opening agent;

[0016] The modified isocyanate prepolymer B comprises the following components:

[0017] (e) urethane-modified isocyanate, which is a product obtained by reacting a polyether polyol (e1) having an average functionality of 2 to 3 (e.g., 2.5) with an isocyanate (e2);

[0018] (f) Carbodiimide-modified isocyanate.

[0019] According to the polyurethane foam material provided by the present invention, in some embodiments, the cell opener is polybutadiene.

[0020] In some embodiments, in the polyether polyol composition A, the combination of auxiliary agents further includes: a blowing agent, a catalyst, a chain extender, and optionally a color paste.

[0021] In some embodiments, in the polyether polyol composition A, based on the total weight of the polyether polyol component (a), the polyether polyol component (b) and the polyether polyol component (c), the weight of each component is as follows:

[0022] Polyether polyol component (a), 30-65 parts, for example, 32 parts, 34 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 64 parts;

[0023] Polyether polyol component (b), 4-20 parts, for example, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 18 parts;

[0024] Polyether polyol component (c), 20-50 parts, for example, 22 parts, 24 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 48 ​​parts;

[0025] Blowing agent, 0.6-2 parts, for example, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.8 parts;

[0026] Catalyst, 0.3-2.1 parts, for example, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.8 parts, 2.0 parts;

[0027] Chain extender, 2-6 parts, for example, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 5 parts, 5.5 parts;

[0028] Color paste, 0-6 parts, for example, 0.1 parts, 0.5 parts, 1 parts, 2 parts, 4 parts, 5 parts, 5.5 parts;

[0029] Cell opener, 2-4 parts, for example, 2.5 parts, 3 parts, 3.5 parts.

[0030] In some embodiments, the blowing agent is selected from one or more of H2O, liquid CO2, formic acid and chlorofluorocarbon compounds, preferably H2O.

[0031] In some embodiments, the chain extender is selected from one or more of ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, and dipropylene glycol.

[0032] In some embodiments, the catalyst is selected from an amine catalyst and / or a tin catalyst; preferably, the amine catalyst is selected from one or more of bis(dimethylaminoethyl) ether, triethylenediamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine and dimethylethanolamine, and the tin catalyst is selected from one or more of stannous octoate and dibutyltin dilaurate.

[0033] In some embodiments, the color paste is selected from one or more of white color paste, red color paste, orange color paste, yellow color paste, green color paste, blue color paste, purple color paste and black color paste.

[0034] According to the polyurethane foam material provided by the present invention, in some embodiments, in the modified isocyanate prepolymer B, the polyether polyol (e1) comprises the following components:

[0035] (g) a polyether polyol, which accounts for 50 wt % to 80 wt % (e.g., 52 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %) of the total weight of the polyether polyol component (e1), has an average functionality of 2 to 3 (e.g., 2.5), a number average molecular weight of 1000 to 8000 (e.g., 1500, 2000, 2500, 3000, 3200, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500), and a hydroxyl value of 14.0 mgKOH / g to 180 mgKOH / g (e.g., 20 mgKOH / g, 30 mgKOH / g, 40 mgKOH / g, 50 mgKOH / g, 60 mgKOH / g, 80 mgKOH / g, 90 mgKOH / g, 100 mgKOH / g, 120 mgKOH / g, 140 mgKOH / g, 150 mgKOH / g, 165 mgKOH / g, 170 mgKOH / g); its ethylene oxide content is 2 wt% to 18 wt% (e.g., 4 wt%, 5 wt%, 10 wt%, 15 wt%);

[0036] (h) a polyether polyol, which accounts for 20 wt% to 50 wt% (e.g., 22 wt%, 24 wt%, 25 wt%, 28 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%) of the total weight of the polyether polyol component (e1), has an average functionality of 2-3, a number average molecular weight of 300 to 1000 (e.g., 320, 340, 350, 400, 500, 600, 700, 800, 900, 950), and a hydroxyl value of 160 mg KOH / g to 350mgKOH / g (for example, 165mgKOH / g, 180mgKOH / g, 200mgKOH / g, 250mgKOH / g, 300mgKOH / g, 340mgKOH / g); its ethylene oxide content is 0 to 10wt% (for example, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 4.5wt%, 5wt%, 6wt%, 8wt%, 9wt%).

[0037] In some embodiments, in the modified isocyanate prepolymer B, the isocyanate component (e2) is MDI 100 produced by Wanhua Chemical.

[0038] In some embodiments, in the modified isocyanate prepolymer B, the carbodiimide-modified isocyanate component (f) is CDMDI100L produced by Wanhua Chemical.

[0039] In some embodiments, the urethane-modified isocyanate component (e) accounts for 70-90 wt% (e.g., 72 wt%, 75 wt%, 80 wt%, 85 wt%, 88 wt%) of the total weight of the modified isocyanate prepolymer B; the carbodiimide-modified isocyanate component (f) accounts for 10-30 wt% (e.g., 12 wt%, 14 wt%, 15 wt%, 18 wt%, 20 wt%, 24 wt%, 25 wt%, 28 wt%) of the total weight of the modified isocyanate prepolymer B.

[0040] In some embodiments, the NCO content of the modified isocyanate prepolymer B is 12-24 wt%, for example, 14 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%.

[0041] According to the polyurethane foam material provided by the present invention, in some embodiments, the weight ratio of the polyether polyol composition A to the modified isocyanate prepolymer B is 100:(35-65); for example, 100:38, 100:40, 100:42, 100:45, 100:50, 100:55, 100:60, 100:62, 100:64.

[0042] According to the polyurethane foam material provided by the present invention, in some embodiments, the density of the polyurethane foam material is 90 to 160 kg / m 3 , ASKER F hardness is 60 to 95, the compression permanent deformation tested according to ASTM D-395-B standard is less than or equal to 5%, the ball rebound rate tested according to ASTM D3574 standard is less than or equal to 10%, and the air permeability is greater than or equal to 10L / min. Polyurethane foam material has good air permeability and comfort.

[0043] In a second aspect, a method for preparing the polyurethane foam material as described above is provided, comprising the following steps:

[0044] (1) mixing the polyether polyol component (a), the polyether polyol component (b), the polyether polyol component (c) and the combination auxiliary agent as the component (d) to obtain the polyether polyol composition A;

[0045] (2) reacting the polyether polyol component (e1) with the isocyanate component (e2) at 70-90° C. (e.g., 75° C., 80° C., 85° C.) for 1-5 h (e.g., 2 h, 3 h, 4 h), and adding the carbodiimide-modified isocyanate component (f) to the system according to the requirements of NCO content and viscosity index to obtain the modified isocyanate prepolymer B;

[0046] (3) After the polyether polyol composition A obtained in step (1) and the modified isocyanate prepolymer B obtained in step (2) are mixed evenly (for example, they can be mixed manually or mechanically; the raw material mixing temperature is 20 to 25° C., and the mixing time is 2 to 25 seconds), the resulting mixture is poured into a mold (for example, the mold temperature is 30 to 35° C.), and then matured for 20 to 25 minutes; after the mold is opened, the pores are physically opened, and after aging for 12 to 24 hours, the polyurethane foam material is obtained.

[0047] According to the preparation method provided by the present invention, in some embodiments, the physical opening method is mechanical rolling, and the foam product obtained after mold opening is mechanically rolled to 15-30% (such as 18%, 20%, 25%) of its initial thickness.

[0048] According to the preparation method provided by the present invention, in some embodiments, in step (1), the mixing process conditions include: each component is stirred for 8 to 15 minutes by a high-speed shear mixer, the stirring speed is 1000 to 2000 rpm, and the stirring temperature is 5 to 30°C.

[0049] In some embodiments, in step (2), the raw materials can be stirred and mixed at a speed of 600-2000 rpm.

[0050] In a third aspect, there is provided a use of the polyurethane foam material as described above or the polyurethane foam material prepared by the preparation method as described above in a breathable slow-rebound insole.

[0051] In the present invention, the operating steps and specific process conditions of the application can be conventionally selected in the art and will not be described in detail here.

[0052] Compared with the prior art, the beneficial effects of the technical solution of the present invention are at least:

[0053] By controlling and selecting parameters such as the molecular weight, hydroxyl value, and ethylene oxide content of the polyether polyol c in the polyether polyol composition A (A material), controlling and selecting parameters such as the molecular weight, hydroxyl value, and ethylene oxide content of the polyether polyol h selected in the modified isocyanate (B material), and improving the foam preparation process by adding a cell-opening agent and physically opening cells after mold opening, the preparation method of the present invention is simple in process, the combined material can be stably stored at room temperature and is free of crystallization, and the obtained polyurethane foam material has the advantages of slow rebound and breathability, thereby improving the air permeability and / or compression deformation performance of the slow rebound polyurethane foam. DETAILED DESCRIPTION

[0054] In order to understand the technical features and content of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the embodiments, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein. For those who do not specify specific conditions in the embodiments, they are carried out according to normal conditions or the conditions recommended by the manufacturer.

[0055] The main raw material sources of the present invention are as follows. Other raw materials are common commercially available raw materials unless otherwise specified:

[0056] (Polyether polyol ac)

[0057] Polyether polyol-1: a copolymerized polyether polyol prepared with propylene oxide and propylene oxide as monomers and 15 wt% ethylene oxide content, 4800 molecular weight, functionality 3, and 35.1 mgKOH / g of hydroxyl value;

[0058] Polyether polyol-2: using propylene glycol as the initiator, styrene and acrylonitrile copolymerized grafted modified polyether polyol, with a solid content of 30wt%, a molecular weight of 5000, a functionality of 3, and a hydroxyl value of 21.0mgKOH / g;

[0059] Polyether polyol-3: a copolymerized polyether polyol with propylene glycol and propylene glycol as initiators, ethylene oxide and propylene oxide as monomers, with an ethylene oxide content of 5wt%, a molecular weight of 500, a functionality of 2.5, and a hydroxyl value of 280.5mgKOH / g;

[0060] (Polyether polyol c')

[0061] Polyether polyol-4': a copolymerized polyether polyol with propylene glycol and propylene glycol as initiators, ethylene oxide and propylene oxide as monomers, with an ethylene oxide content of 5wt%, a molecular weight of 2000, and a functionality of 2.5. Hydroxyl value: 70.1mgKOH / g ;

[0062] Polyether polyol-5': a copolymerized polyether polyol with propylene glycol and propylene glycol as initiators and ethylene oxide and propylene oxide as monomers. Ethylene oxide content: 10wt% , molecular weight is 500, functionality is 2.5, and hydroxyl value is 280.5mgKOH / g;

[0063] (G component and H component of polyether polyol e1 in modified isocyanate)

[0064] Polyether polyol-6: a copolymerized polyether polyol with propylene glycol as the initiator, ethylene oxide and propylene oxide as monomers, with an ethylene oxide content of 5wt%, a molecular weight of 4000, a functionality of 2, and a hydroxyl value of 28.1mgKOH / g;

[0065] Polyether polyol-7: a copolymerized polyether polyol with propylene glycol and propylene glycol as initiators, ethylene oxide and propylene oxide as monomers, with an ethylene oxide content of 10wt%, a molecular weight of 700, a functionality of 2.5, and a hydroxyl value of 200.4mgKOH / g;

[0066] (Polyether polyol h')

[0067] Polyether polyol-8': a copolymerized polyether polyol with propylene glycol and propylene glycol as initiators and ethylene oxide and propylene oxide as monomers. Ethylene oxide content: 15wt% , molecular weight is 700, functionality is 2.5, and hydroxyl value is 200.4mgKOH / g;

[0068] Preparation method of modified isocyanate prepolymer B (calculated based on 1000g of the final product)

[0069] Preparation of modified isocyanate prepolymer B-1: Add 450g of diphenylmethane diisocyanate (Wanhua Chemical, MDI-100) into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen tube, heat to 60-70°C, then add 200g of polyether polyol-6 and 120g of polyether polyol-7, and react at 80°C for 2h, cool to below 40°C, and then add 230g of carbodiimide modified isocyanate (Wanhua Chemical, CDMDI100L) to obtain a modified isocyanate prepolymer B-1 with an NCO mass fraction controlled at 19.1-20.1wt%;

[0070] Preparation of modified isocyanate prepolymer B-2': 450 g of diphenylmethane diisocyanate (Wanhua Chemical, MDI-100) was added to a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen tube, heated to 60-70°C, and then 200 g of polyether polyol-6 and 120 g of Polyether polyol-8' After reacting at 80°C for 2h, the temperature was lowered to below 40°C and 230g of carbodiimide modified isocyanate (Wanhua Chemical, CDMDI100L) was added. The NCO mass fraction of the modified isocyanate prepolymer B-2' was controlled at 19.1-20.1wt%;

[0071] Preparation of modified isocyanate prepolymer B-3: Add 450g of diphenylmethane diisocyanate (Wanhua Chemical, MDI-100) into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen tube, heat to 60-70°C, then add 256g of polyether polyol-6 and 64g of polyether polyol-7, and react at 80°C for 2h, cool to below 40°C, and then add 230g of carbodiimide modified isocyanate (Wanhua Chemical, CDMDI100L). The NCO mass fraction of the modified isocyanate prepolymer B-3 is controlled at 22.1-23.1wt%;

[0072] Preparation of modified isocyanate prepolymer B-4: Add 450g of diphenylmethane diisocyanate (Wanhua Chemical, MDI-100) into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen tube, heat to 60-70°C, then add 160g of polyether polyol-6 and 160g of polyether polyol-7, and react at 80°C for 2h, cool to below 40°C, and then add 230g of carbodiimide modified isocyanate (Wanhua Chemical, CDMDI100L). The NCO mass fraction of the modified isocyanate prepolymer B-4 is controlled at 18.1-19.1wt%.

[0073] Color paste was purchased from Shanghai Baomeishi.

[0074] Preparation of polyurethane insole foam

[0075] Example 1

[0076] At room temperature, the raw materials of polyether polyol composition A were sequentially placed into a reaction kettle according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged as polyether polyol composition A1.

[0077] The polyether polyol composition A1 and the modified isocyanate prepolymer B-1 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and the mold was opened after aging for 20 minutes. The polyurethane foam material was then placed at room temperature for 24 hours to obtain its mechanical properties.

[0078] Example 2

[0079] At room temperature, the raw materials of polyether polyol composition A were placed into a reaction kettle in sequence according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged as polyether polyol composition A5.

[0080] The polyether polyol composition A5 and the modified isocyanate prepolymer B-1 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and the mold was opened after aging for 20 minutes. The polyurethane foam material was then placed at room temperature for 24 hours to obtain its mechanical properties.

[0081] Example 3

[0082] At room temperature, the raw materials of polyether polyol composition A were placed into a reaction kettle in sequence according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged to obtain polyether polyol composition A6.

[0083] The polyether polyol composition A6 and the modified isocyanate prepolymer B-1 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and the mold was opened after aging for 20 minutes. The polyurethane foam material was then placed at room temperature for 24 hours to obtain its mechanical properties.

[0084] Example 4

[0085] At room temperature, the raw materials of polyether polyol composition A were placed into a reaction kettle in sequence according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged to obtain polyether polyol composition A7.

[0086] The polyether polyol composition A7 and the modified isocyanate prepolymer B-1 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and the mold was opened after aging for 20 minutes. The polyurethane foam material was then placed at room temperature for 24 hours to obtain its mechanical properties.

[0087] Example 5

[0088] At room temperature, the raw materials of polyether polyol composition A were sequentially placed into a reaction kettle according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged as polyether polyol composition A1.

[0089] The polyether polyol composition A1 and the modified isocyanate prepolymer B-3 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and the mold was opened after aging for 20 minutes. The polyurethane foam material was then placed at room temperature for 24 hours to obtain its mechanical properties.

[0090] Example 6

[0091] At room temperature, the raw materials of polyether polyol composition A were sequentially placed into a reaction kettle according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged as polyether polyol composition A1.

[0092] The polyether polyol composition A1 and the modified isocyanate prepolymer B-4 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and opened after aging for 20 minutes. The mold was then physically opened by mechanical rolling, and the polyurethane foam material was obtained after being placed at room temperature for 24 hours, and its mechanical properties were tested.

[0093] Comparative Example 1

[0094] At room temperature, the raw materials of polyether polyol composition A were placed into a reaction kettle in sequence according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged as polyether polyol composition A2.

[0095] The polyether polyol composition A2 and the modified isocyanate prepolymer B-1 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and opened after aging for 20 minutes. The mold was then physically opened by mechanical rolling, and the polyurethane foam material was obtained after being placed at room temperature for 24 hours, and its mechanical properties were tested.

[0096] Comparative Example 2

[0097] At room temperature, the raw materials of polyether polyol composition A were sequentially placed into a reaction kettle according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged as polyether polyol composition A1.

[0098] The polyether polyol composition A1 and the modified isocyanate prepolymer B-2' were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and opened after aging for 20 minutes. The mold was then physically opened by mechanical rolling, and the polyurethane foam material was obtained after being placed at room temperature for 24 hours, and its mechanical properties were tested.

[0099] Comparative Example 3

[0100] At room temperature, the raw materials of polyether polyol composition A were sequentially placed into a reaction kettle according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged as polyether polyol composition A1.

[0101] The polyether polyol composition A1 and the modified isocyanate prepolymer B-1 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and the mold was opened after aging for 20 minutes. The molded product was placed at room temperature for 24 hours without mechanical rolling to obtain the polyurethane foam material, and its mechanical properties were tested.

[0102] Comparative Example 4

[0103] At room temperature, the raw materials of polyether polyol composition A were placed into a reaction kettle in sequence according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged as polyether polyol composition A3.

[0104] The polyether polyol composition A3 and the modified isocyanate prepolymer B-1 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and the mold was opened after aging for 20 minutes. The polyurethane foam material was then placed at room temperature for 24 hours to obtain its mechanical properties.

[0105] Comparative Example 5

[0106] At room temperature, the raw materials of polyether polyol composition A were placed into a reaction kettle in sequence according to the formula shown in Table 1, and stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 1500 rpm. After mixing evenly, the materials were discharged as polyether polyol composition A4.

[0107] The polyether polyol composition A4 and the modified isocyanate prepolymer B-1 were mixed and stirred at 21°C according to the ratio shown in Table 1, and mixed by hand for 20 seconds to be uniformly mixed. The resulting mixture was then poured into a mold at 32°C, and the mold was opened after aging for 20 minutes. The polyurethane foam material was then placed at room temperature for 24 hours to obtain its mechanical properties.

[0108] The foam materials prepared in the above embodiments and comparative examples were subjected to sample testing according to ASTM standards. The test results are shown in Table 1.

[0109]

[0110]

[0111] The properties of the polyurethane foams provided in the above embodiments and comparative examples were tested, and the testing method was as follows:

[0112] Air permeability: Use an air flow tester with a fixed pressure of 125Pa to test air permeability in L / min.

[0113] Density: According to standard ASTM D-792;

[0114] Hardness (ASKER F): According to standard ASTM D-2240;

[0115] Drop ball rebound: according to ASTM D3574;

[0116] Compression set: According to ASTM D-395-B.

[0117] From the results in Table 1, it can be seen that by designing the raw materials for preparing polyurethane foam, a polyether polyol component a with a specific ethylene oxide content and molecular weight is selected to be used in combination with other two polyether polyols to obtain a polyether polyol composition, and a specific isocyanate component is matched, and a polyurethane foam insole with high air permeability and slow rebound is prepared by combining a physical opening method. The air permeability is in the range of 14.3-22.2 L / min, and the density is 118-140 kg / m 3 Within the range, the hardness is within the range of 70~88F, the ball drop rebound rate is ≤10%, and the compression permanent deformation is ≤5%.

[0118] From the comparison between Example 1 and Comparative Example 1, it can be seen that if a special cell-opening agent is not selected, the air permeability of the prepared polyurethane foam insole is poor and the compression deformation resistance is also poor.

[0119] From the comparison between Example 1 and Comparative Example 2, it can be seen that if the modified isocyanate prepolymer prepared by using polyether polyol (h) with too high ethylene oxide content is used, the air permeability of the prepared polyurethane foam insole is poor and the compression deformation resistance is also poor.

[0120] By comparing Example 1 with Comparative Example 3, it can be seen that the present invention uses mechanical rolling to perform physical pore opening to prepare a polyurethane foam insole with excellent performance, while Comparative Example 3 does not use mechanical rolling to perform physical pore opening, and the prepared polyurethane foam insole has poor air permeability.

[0121] From the comparison between Example 1 and Comparative Example 4, it can be seen that when preparing the polyether polyol composition, if a high molecular weight polyether polyol is selected as the polyether polyol component c, the resilience of the prepared polyurethane foam cannot meet the slow rebound requirement and the air permeability is also poor.

[0122] From the comparison between Example 1 and Comparative Example 5, it can be seen that when preparing the polyether polyol composition, if a polyether polyol with too high an ethylene oxide content is selected as the polyether polyol component c, the prepared polyurethane foam cannot meet the requirements for resilience, and has poor air permeability and compression permanent deformation properties.

[0123] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the spirit of the present invention.

Claims

1. A polyurethane foam material, which is a product obtained by reacting a polyether polyol composition A and a modified isocyanate prepolymer B; characterized in that: The polyether polyol composition A comprises: a polyether polyol mixture and a combination auxiliary agent; wherein, The polyether polyol mixture comprises the following components: (a) a polyether polyol having an average functionality of 2 to 4, a number average molecular weight of 2000 to 8000, a hydroxyl value of 18 mgKOH / g to 80 mgKOH / g, and an ethylene oxide content of 2 wt % to 18 wt %; (b) polyether polyol, a product obtained by copolymerization and grafting modification of styrene and acrylonitrile, having a solid content of 20wt% to 45wt%, an average functionality of 2 to 4, a number average molecular weight of 2000 to 5000, a hydroxyl value of 18mgKOH / g to 80mgKOH / g; and an ethylene oxide content of 2wt% to 18wt%; (c) a polyether polyol having an average functionality of 2 to 4, a number average molecular weight of 300 to 1000, a hydroxyl value of 160 to 350 mgKOH / g, and an ethylene oxide content of 0 to 5 wt %; The combination of auxiliary agents at least includes a cell-opening agent; The modified isocyanate prepolymer B comprises the following components: (e) urethane-modified isocyanate, which is a product obtained by reacting a polyether polyol (e1) having an average functionality of 2 to 3 with an isocyanate (e2); (f) Carbodiimide-modified isocyanate.

2. The polyurethane foam material according to claim 1, characterized in that The cell opening agent is polybutadiene.

3. The polyurethane foam material according to claim 1 or 2, characterized in that: In the polyether polyol composition A, the combination of auxiliary agents further includes: a foaming agent, a catalyst, a chain extender and optional color paste.

4. The polyurethane foam material according to claim 3, characterized in that: In the polyether polyol composition A, based on the total weight of the polyether polyol component (a), the polyether polyol component (b) and the polyether polyol component (c), the weight of each component is as follows: Polyether polyol component (a), 30-65 parts; Polyether polyol component (b), 4-20 parts; Polyether polyol component (c), 20-50 parts; Foaming agent, 0.6-2 parts; Catalyst, 0.3-2.1 parts; Chain extender, 2-6 parts; Color paste, 0-6 parts; Cell opener, 2-4 parts.

5. The polyurethane foam material according to claim 3 or 4, characterized in that: The foaming agent is selected from one or more of H2O, liquid CO2, formic acid and chlorofluorocarbon compounds, preferably H2O; The chain extender is selected from one or more of ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol and dipropylene glycol; The catalyst is selected from amine catalysts and / or tin catalysts; preferably, the amine catalyst is selected from one or more of bis(dimethylaminoethyl) ether, triethylenediamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine and dimethylethanolamine, and the tin catalyst is selected from one or more of stannous octoate and dibutyltin dilaurate.

6. The polyurethane foam material according to any one of claims 1 to 5, characterized in that: In the modified isocyanate prepolymer B, the polyether polyol (e1) comprises the following components: (g) a polyether polyol, which accounts for 50 wt% to 80 wt% of the total weight of the polyether polyol component (e1), has an average functionality of 2 to 3, a number average molecular weight of 1000 to 8000, a hydroxyl value of 14.0 mgKOH / g to 180 mgKOH / g; and an ethylene oxide content of 2 wt% to 18 wt%; (h) polyether polyol, which accounts for 20 wt% to 50 wt% of the total weight of the polyether polyol component (e1), has an average functionality of 2-3, a number average molecular weight of 300 to 1000, a hydroxyl value of 160 mgKOH / g to 350 mgKOH / g; and an ethylene oxide content of 0 to 10 wt%.

7. The polyurethane foam material according to any one of claims 1 to 6, characterized in that: The urethane modified isocyanate component (e) accounts for 70-90wt% of the total weight of the modified isocyanate prepolymer B; the carbodiimide modified isocyanate component (f) accounts for 10-30wt% of the total weight of the modified isocyanate prepolymer B; The modified isocyanate prepolymer B has an NCO content of 12-24 wt%.

8. The polyurethane foam material according to any one of claims 1 to 7, characterized in that: The weight ratio of the polyether polyol composition A to the modified isocyanate prepolymer B is 100:(35-65).

9. The polyurethane foam material according to any one of claims 1 to 8, characterized in that: The density of the polyurethane foam material is 90 to 160 kg / m 3 , ASKER F hardness is 60 to 95, the compression set tested according to ASTM D-395-B standard is less than or equal to 5%, the ball rebound rate tested according to ASTM D3574 standard is less than or equal to 10%, and the air permeability is greater than or equal to 10L / min.

10. The method for preparing a polyurethane foam material according to any one of claims 1 to 9, characterized in that: The following steps are involved: (1) mixing the polyether polyol component (a), the polyether polyol component (b), the polyether polyol component (c) and the combination auxiliary agent as the component (d) to obtain the polyether polyol composition A; (2) reacting the polyether polyol component (e1) with the isocyanate component (e2) at 70-90° C. for 1-5 hours, and adding the carbodiimide modified isocyanate component (f) to the system according to the requirements of NCO content and viscosity index to obtain the modified isocyanate prepolymer B; (3) after uniformly mixing the polyether polyol composition A obtained in step (1) and the modified isocyanate prepolymer B obtained in step (2), pouring the obtained mixture into a mold, and then ripening for 20 to 25 minutes; after opening the mold, physically opening the mold, and ripening for 12 to 24 hours to obtain the polyurethane foam material; Preferably, the physical opening method is mechanical rolling, and the foam product obtained after mold opening is mechanically rolled to 15-30% of its initial thickness.

11. Use of the polyurethane foam material according to any one of claims 1 to 9 or the polyurethane foam material prepared by the preparation method according to claim 10 in a breathable slow-rebound insole.

Images