Polyurethane foam material and preparation method and application thereof

Abstract

The present invention relates to a polyurethane foam material and a preparation method and application thereof. The polyurethane foam material is obtained by reacting a polyether polyol composition and a modified isocyanate prepolymer; the polyether polyol composition comprises three different polyether polyols, and the mass content of ethylene oxide in the preparation raw materials of the three different polyether polyols is independently less than 50%. The polyurethane foam material of the present invention has the characteristics of low density, high hardness, low compression permanent deformation and high ball rebound, and has excellent mechanical properties such as elongation at break and tear strength, which is conducive to the preparation of insoles using a traditional infusion process.

Description

Technical Field

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

[0002] At present, the mainstream insole material EVA (ethylene-vinyl acetate copolymer) has poor compression deformation and poor service life. It is an inevitable trend in the field of sports insoles to replace EVA with polyurethane insoles.

[0003] At present, there are three main processes for preparing polyurethane materials for insoles:

[0004] The first is the breathable insole process, the product density is 100-160kg / m 3 The advantage of this type of product is that it has good air permeability, the insole can "breathe" freely, and is not easy to have foot odor. For example, CN106632985A discloses a method for preparing a breathable polyurethane insole material. CN101585901B discloses a polyurethane foam material and its preparation method and use. What is obtained is a plate (2 meters long, 1.1-1.4 meters wide, 0.12-0.16 meters high), which is obtained by flat cutting to obtain sheets, and by vertical cutting to obtain a pair of insoles-sized sheets. The material needs to be further hot-pressed to stabilize the shape and the edges and corners need to be cut to obtain the insole; this product is more wasteful, there is waste on the raw material end, and there is waste on the foam scraps. Calculated from the source, the effective utilization rate is only 65-70%;

[0005] The second is the split insole process, the product density is 130-200kg / m 3 This type of product requires the preparation of a molded test piece first, which is then cut or obliquely cut, pasted, hot-pressed to stabilize the shape, and cut off the edges and corners. This type of product has moderate air permeability and has a certain improvement in elasticity compared to the air permeability process. The effective utilization rate of the product is 80-90%. CN111447851A discloses a method for preparing a breathable polyurethane insole material.

[0006] The third is the molding and injection process, the product density is 240-350kg / m 3 This process is a one-time injection molding, eliminating the hot pressing and trimming processes, and there is little waste, and the effective utilization rate can be over 90%. The upper and lower surfaces of the product form a dense skin, and the material appearance is good. At present, the biggest problem of this product is that the density is significantly higher than that of the other two processes, and the insoles produced are heavy, which affects the application of such products in sports shoes that pursue lightweight.

[0007] The industry has tried to reduce the density of injected insoles. However, if the hardness is maintained after the density is reduced, the common practice in the industry is to increase the amount of chain extender, water and isocyanate, resulting in deviations in product elasticity and compression permanent deformation. For example, the density is reduced from 280 to 220 kg / m3 The hardness is 30ASKER C, the ball rebound is reduced from 45 to less than 30%, and the compression set is increased from 5% to more than 10%. The rebound directly determines the support and comfort of the insole, while the larger compression set directly affects the life of the insole.

[0008] Therefore, it is crucial to develop a polyurethane foam material with high elasticity, excellent compression permanent deformation and lightweight, so that when using the traditional infusion process to prepare insoles, the loss of the infusion process can be maintained at a low level, the problem of high product density caused by the infusion process can be solved, and the purpose of lightweighting the product can be achieved. Summary of the invention

[0009] In view of the deficiencies in the prior art, the object of the present invention is to provide a polyurethane foam material and a preparation method and application thereof. The polyurethane foam material has the characteristics of low density, high hardness, low compression permanent deformation and high ball rebound, and has excellent mechanical properties such as elongation at break and tear strength, which is conducive to the preparation of insoles using traditional infusion technology.

[0010] To achieve this object, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides a polyurethane foam material, wherein the polyurethane foam material is obtained by reacting a polyether polyol composition and a modified isocyanate prepolymer;

[0012] The polyether polyol composition comprises three different polyether polyols, wherein the mass content of ethylene oxide in the raw materials for preparing the three different polyether polyols is independently less than 50%, for example, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, etc.

[0013] When the polyurethane foam material is prepared into an insole product, the openness of the insole product is related to the phase separation degree of the polyurethane foam material itself; the higher the phase separation degree, the greater the product openness, and vice versa; NCO groups react with water to generate urea, and the urea-rich hard segments of different molecules aggregate into urea phase hard regions due to hydrogen bonding, and microphase separation occurs due to the thermodynamic incompatibility of soft and hard segments, but the microphase separation is generally incomplete, that is, a small amount of hard segments are dispersed in the soft segment phase, which leads to a poor phase separation degree and an increase in the glass transition temperature of the soft segment phase. In the present invention, the polyurethane foam material includes three polyether polyols, wherein the mass content of ethylene oxide is less than 50%, and the soft segment phase contains a large amount of oxyethylene groups, which can dissolve part of the urea phase (but at the same time, the reduction of urea hardness leads to physical property deviation), so that the soft segment phase is purer, the higher the phase separation degree, the better the openness of the product. In the present invention, the modified isocyanate prepolymer is combined with the polyether polyol with a specific ethylene oxide content to combine the open porosity and physical properties. Therefore, the polyurethane foam material described in the present invention has the characteristics of low density, high hardness, low compression permanent deformation and high ball rebound, and has excellent mechanical properties such as elongation at break and tear strength, which is conducive to the preparation of insoles using traditional infusion technology.

[0014] In the present invention, the first polyether polyol, the second polyether polyol and the third polyether polyol are copolymerized polyether polyols of ethylene oxide and propylene oxide, and the “mass content of ethylene oxide” refers to the content of ethylene oxide therein.

[0015] Preferably, the average functionality of the first polyether polyol is 2-4, such as 2.5, 3, 3.5, etc.

[0016] Preferably, the number average molecular weight of the first polyether polyol is 2000-8000 g / mol, for example, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, etc.

[0017] Preferably, the hydroxyl value of the first polyether polyol is 14-112.2 mgKOH / g, for example, 20 mgKOH / g, 40 mgKOH / g, 60 mgKOH / g, 80 mgKOH / g, 100 mgKOH / g, etc.

[0018] Preferably, the raw material for preparing the first polyether polyol includes 10%-20% by weight of ethylene oxide, such as 12%, 14%, 16%, 18%, etc. Preferably, the second polyether polyol is obtained by copolymerization and grafting modification of styrene and acrylonitrile.

[0019] Preferably, the solid content of the second polyether polyol is 20%-45%, such as 25%, 30%, 40%, etc.

[0020] Preferably, the average functionality of the second polyether polyol is 2-4, such as 2.5, 3, 3.5, etc.

[0021] Preferably, the number average molecular weight of the second polyether polyol is 2000-8000 g / mol, for example, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, etc.

[0022] Preferably, the hydroxyl value of the second polyether polyol is 14-112.2 mgKOH / g, for example, 20 mgKOH / g, 40 mgKOH / g, 60 mgKOH / g, 80 mgKOH / g, 100 mgKOH / g, etc.

[0023] Preferably, the raw material for preparing the second polyether polyol includes ethylene oxide in an amount of 10% to 20% by weight, such as 12%, 14%, 16%, 18%, etc.

[0024] In the present invention, the mass content of ethylene oxide is calculated based on the total mass of ethylene oxide and propylene oxide in the second polyether polyol as 100%.

[0025] Preferably, the average functionality of the third polyether polyol is 2-4, such as 2.5, 3, 3.5, etc.

[0026] Preferably, the number average molecular weight of the third polyether polyol is 1000-8000 g / mol, for example, 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, etc.

[0027] Preferably, the hydroxyl value of the third polyether polyol is 14-112.2 mgKOH / g, for example, 20 mgKOH / g, 40 mgKOH / g, 60 mgKOH / g, 80 mgKOH / g, 100 mgKOH / g, etc.

[0028] Preferably, the raw material for preparing the third polyether polyol includes ethylene oxide with a mass content of less than 50%, such as 45%, 40%, 35%, 30%, 25%, etc., more preferably 30%-50%, and not equal to 50%.

[0029] In the present invention, the third polyether polyol is a polyether polyol with a high ethylene oxide content, so that the soft segment phase contains a large number of ethylene oxide groups, which can dissolve part of the urea phase (but at the same time, the hardness of the urea group is reduced, resulting in physical property deviations), making the soft segment phase purer, the higher the degree of phase separation, and the better the open porosity of the product.

[0030] Preferably, in the third polyether polyol preparation raw material, the mass content of ethylene oxide is 30%-50%, and is not equal to 50%, for example, 35%, 40%, 45%, etc.

[0031] Preferably, the polyether polyol composition further comprises an auxiliary agent.

[0032] Preferably, the auxiliary agent includes any one of a foaming agent, a catalyst, a chain extender or a color paste, or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of a foaming agent and a catalyst, a combination of a catalyst, a chain extender and a color paste, a combination of a foaming agent, a catalyst, a chain extender and a color paste, etc.

[0033] Preferably, based on the total mass of the polyether polyol composition as 100%, the mass percentage of the first polyether polyol is 40%-95%, for example 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% and the like.

[0034] Preferably, based on the total mass of the polyether polyol composition as 100%, the mass percentage of the second polyether polyol is 5%-50%, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc.

[0035] Preferably, based on the total mass of the polyether polyol composition as 100%, the mass percentage of the third polyether polyol is 0.5%-10%, for example, 1%, 2%, 4%, 6%, 8% and the like.

[0036] Preferably, based on the total mass of the polyether polyol composition being 100%, the mass percentage of the auxiliary agent is 0%-22%, for example, 2%, 5%, 10%, 15%, 20%, etc.

[0037] Preferably, based on the total mass of the polyether polyol composition being 100%, the mass percentage of the foaming agent is 1%-10%, for example, 2%, 4%, 6%, 8%, etc.

[0038] Preferably, based on the total mass of the polyether polyol composition being 100%, the mass percentage of the catalyst is 0.2%-2%, such as 0.5%, 1%, 1.5%, etc.

[0039] Preferably, based on the total mass of the polyether polyol composition as 100%, the mass percentage of the chain extender is 0%-5%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.

[0040] Preferably, based on the total mass of the polyether polyol composition as 100%, the mass percentage of the color paste is 0%-5%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.

[0041] Preferably, the blowing agent comprises any one of water, liquid carbon dioxide, chlorofluorocarbon compounds or hydrochlorofluorocarbon compounds, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of water and liquid carbon dioxide, a combination of liquid carbon dioxide and chlorofluorocarbon compounds, a combination of chlorofluorocarbon compounds and hydrochlorofluorocarbon compounds, a combination of water, liquid carbon dioxide, chlorofluorocarbon compounds and hydrochlorofluorocarbon compounds, and the like.

[0042] Preferably, based on the total mass of the polyether polyol composition as 100%, the mass percentage of water is 1.3%-2.5%, for example, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, etc.

[0043] Preferably, the catalyst comprises an amine catalyst.

[0044] Preferably, the amine catalyst comprises any one of bis(dimethylaminoethyl) ether, triethylenediamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine or dimethylethanolamine, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of bis(dimethylaminoethyl) ether and triethylenediamine, a combination of triethylenediamine, N,N-dimethylcyclohexylamine and pentamethyldiethylenetriamine, a combination of N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine and dimethylethanolamine, and the like.

[0045] Preferably, the chain extender includes any one of methylpropylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol, 1,4-butylene glycol or polyethylene glycol, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of methylpropylene glycol and 1,2-propylene glycol, a combination of 1,3-propylene glycol, diethylene glycol and dipropylene glycol, a combination of diethylene glycol, dipropylene glycol, ethylene glycol, 1,4-butylene glycol and polyethylene glycol, and the like.

[0046] Preferably, the number average molecular weight of the polyethylene glycol is 200-1000 g / mol, such as 400 g / mol, 600 g / mol, 800 g / mol, etc.

[0047] Preferably, the color paste includes any one of red color paste, orange color paste, yellow color paste, green color paste, blue color paste, purple color paste or black color paste, or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of red color paste, orange color paste and yellow color paste, a combination of green color paste, blue color paste, purple color paste and black color paste, a combination of red color paste, orange color paste, yellow color paste, green color paste, blue color paste, purple color paste and black color paste, etc.

[0048] Preferably, the mass ratio of the polyether polyol composition to the modified isocyanate prepolymer is 100:(40-80), wherein 40-80 can be 15, 50, 55, 60, 65, 70, 75, etc.

[0049] Preferably, in the modified isocyanate prepolymer, the mass percentage of isocyanate is 23%-32%, for example, 24%, 26%, 28%, 30%, etc.

[0050] Preferably, the modified isocyanate prepolymer includes a first modified isocyanate prepolymer, a second modified isocyanate prepolymer and a third modified isocyanate prepolymer.

[0051] Preferably, the first modified isocyanate prepolymer comprises urethane-modified isocyanate.

[0052] Preferably, the urethane-modified isocyanate is obtained by reacting a polyol with an isocyanate, wherein the isocyanate can be selected from MDI100 produced by Wanhua Chemical.

[0053] Preferably, the average functionality of the polyol is 2-3, such as 2.2, 2.4, 2.6, 2.8, etc.

[0054] Preferably, the polyol includes a fourth polyether polyol, a fifth polyether polyol and a sixth polyether polyol.

[0055] In the present invention, the fourth polyether polyol, the fifth polyether polyol and the sixth polyether polyol are copolymerized polyether polyols of ethylene oxide and propylene oxide, or homopolymerized polyether polyols of propylene oxide, and the “mass content of ethylene oxide” refers to the content of ethylene oxide therein, and the same applies to propylene oxide.

[0056] Preferably, the average functionality of the fourth polyether polyol is 2-3, such as 2.2, 2.4, 2.6, 2.8, etc.

[0057] Preferably, the fourth polyether polyol has a number average molecular weight of 1000-8000 g / mol, for example, 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, etc.

[0058] Preferably, the hydroxyl value of the fourth polyether polyol is 14.0-224.4 mgKOH / g, for example, 20 mgKOH / g, 40 mgKOH / g, 60 mgKOH / g, 80 mgKOH / g, 100 mgKOH / g, 120 mgKOH / g, 140 mgKOH / g, 160 mgKOH / g, 180 mgKOH / g, 200 mgKOH / g, 220 mgKOH / g, etc.

[0059] Preferably, the average functionality of the fifth polyether polyol is 2.

[0060] Preferably, the fifth polyether polyol has a number average molecular weight of 1000-10000 g / mol, for example 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, etc.

[0061] Preferably, the hydroxyl value of the fifth polyether polyol is 11.22-112.2 mgKOH / g, for example, 20 mgKOH / g, 40 mgKOH / g, 60 mgKOH / g, 80 mgKOH / g, 100 mgKOH / g, etc.

[0062] Preferably, the average functionality of the sixth polyether polyol is 2.

[0063] Preferably, the number average molecular weight of the sixth polyether polyol is 1000-10000 g / mol, for example 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, etc.

[0064] Preferably, the hydroxyl value of the sixth polyether polyol is 11.22-112.2 mgKOH / g, for example, 20 mgKOH / g, 40 mgKOH / g, 60 mgKOH / g, 80 mgKOH / g, 100 mgKOH / g, etc.

[0065] Preferably, the raw material for preparing the sixth polyether polyol includes propylene oxide, and the mass content of propylene oxide is 100%.

[0066] In the present invention, when the mass content of propylene oxide is 100%, the sixth polyether polyol is a homopolymerized polyether polyol of propylene oxide.

[0067] Preferably, based on the total mass of the polyol as 100%, the mass percentage of the fourth polyether polyol is 20%-80%, for example, 30%, 40%, 50%, 60%, 70%, etc.

[0068] Preferably, based on the total mass of the polyol as 100%, the mass percentage of the fifth polyether polyol is 10%-70%, for example, 30%, 40%, 50%, 60% and the like.

[0069] Preferably, based on the total mass of the polyol as 100%, the mass percentage of the sixth polyether polyol is 1%-10%, for example, 2%, 4%, 6%, 8% and the like.

[0070] Preferably, the second modified isocyanate prepolymer includes toluene diisocyanate and / or toluene diisocyanate trimer. Wherein, toluene diisocyanate can be selected from TDI-80 or TDI-65 produced by Wanhua Chemical Company, and the toluene diisocyanate trimer can be obtained by self-polymerization reaction of TDI80 or TDI65.

[0071] In the present invention, the second modified isocyanate prepolymer includes toluene diisocyanate and / or toluene diisocyanate trimer. The reason why toluene diisocyanate is preferred is that toluene diisocyanate (TDI) contains one benzene ring in its molecular structure, while diphenylmethane diisocyanate (MDI) contains two benzene rings. The benzene ring is a rigid structure. The higher the benzene ring content, the higher the glass transition temperature of the product. The elasticity and glass transition temperature (T g ) related, T g The lower the glass transition temperature, the higher the elasticity. The lower the glass transition temperature, the more elastic the microporous elastomer is at room temperature, so that it can maintain a very high free-fall rebound at room temperature. Toluene diisocyanate trimer is preferred because TDI is less active than MDI. Increasing the functionality of TDI and using toluene diisocyanate trimer can increase the crosslinking density and thus improve the aging.

[0072] Preferably, the third modified isocyanate prepolymer comprises carbodiimide modified isocyanate, wherein the carbodiimide modified isocyanate can be selected from CDMDI100L produced by Wanhua Chemical.

[0073] Preferably, based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the first modified isocyanate prepolymer is 30%-80%, for example, 40%, 50%, 60%, 70%, etc.

[0074] Preferably, based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the second modified isocyanate prepolymer is 1%-70%, for example, 20%, 30%, 40%, 50%, 60%, etc.

[0075] Preferably, based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the toluene diisocyanate is 10%-50%, for example, 20%, 30%, 40%, etc.

[0076] Preferably, based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the toluene diisocyanate trimer is 1%-20%, such as 5%, 10%, 15%, etc.

[0077] Preferably, based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the third modified isocyanate prepolymer is 10%-30%, such as 15%, 20%, 25%, etc.

[0078] In a second aspect, the present invention provides a method for preparing the polyurethane foam material according to the first aspect, the preparation method comprising the following steps:

[0079] The polyether polyol composition and the modified isocyanate prepolymer are mixed and reacted to obtain a polyurethane foam material.

[0080] Preferably, the mixing temperature is 35-45°C, such as 36°C, 38°C, 40°C, 42°C, 44°C, etc.

[0081] Preferably, the mixing time is 2-8 s, such as 4 s, 6 s, 8 s, etc.

[0082] Preferably, the reaction temperature is 45-55°C, such as 46°C, 48°C, 50°C, 52°C, 54°C, etc.

[0083] Preferably, the reaction time is 4-6 min, such as 4.5 min, 5 min, 5.5 min, etc.

[0084] Preferably, the method for preparing the polyether polyol composition comprises the following steps: mixing a first polyether polyol, a second polyether polyol and a third polyether polyol to obtain a polyether polyol composition.

[0085] Preferably, the mixed raw materials further include auxiliary agents.

[0086] Preferably, the mixing method includes stirring.

[0087] Preferably, the stirring speed is 3000-5000 r / min, such as 3500 r / min, 4000 r / min, 4500 r / min, etc.

[0088] Preferably, the stirring temperature is 10-50°C, for example, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, etc.

[0089] Preferably, the stirring time is 10-30 min, such as 15 min, 20 min, 25 min, etc.

[0090] Preferably, the method for preparing the modified isocyanate prepolymer comprises the following steps: mixing polyol and isocyanate, and reacting them to obtain the modified isocyanate prepolymer.

[0091] Preferably, the reaction is carried out under stirring.

[0092] Preferably, the stirring speed is 10-300 r / min, for example, 50 r / min, 100 r / min, 150 r / min, 200 r / min, 250 r / min, etc.

[0093] Preferably, the reaction temperature is 60-95°C, such as 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc.

[0094] Preferably, the reaction time is 2-4 h, such as 2.5 h, 3 h, 3.5 h, etc.

[0095] In a third aspect, the present invention provides an insole, comprising the polyurethane foam material described in the first aspect.

[0096] Preferably, the insole comprises a poured insole.

[0097] Compared with the prior art, the present invention has the following beneficial effects:

[0098] (1) The polyurethane foam material of the present invention has the characteristics of low density, high hardness, low compression permanent deformation and high ball rebound, and has excellent mechanical properties such as elongation at break and tear strength.

[0099] (2) The density of the polyurethane foam material of the present invention is 140.6-300.2 kg / m 3 The ASKER C hardness is between 28-45, the ball rebound is above 29%, the compression permanent set is within 13.5%, the elongation at break is above 130.6%, and the tear strength is above 3.5%. DETAILED DESCRIPTION

[0100] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0101] In the present invention, the raw materials used in each embodiment are specifically as follows:

[0102] Polyol 1: propylene glycol-based copolymer of ethylene oxide and propylene oxide, 15% ethylene oxide content, number average molecular weight 4800 g / mol, functionality 3, hydroxyl value 35.1 mgKOH / g;

[0103] Polyol 2: trimethylolpropane-based copolymer of ethylene oxide and propylene oxide, 15% ethylene oxide content, number average molecular weight 6000 g / mol, functionality 3, hydroxyl value 28.1 mgKOH / g;

[0104] Polyol 3: Propylene glycol-based, propylene oxide homopolymer polyol, number average molecular weight 6000 g / mol, functionality 2, hydroxyl value 18.7 mgKOH / g

[0105] Polyol 4: Starting from glycerol, a styrene and acrylonitrile copolymer graft modified polyether polyol with a mass ratio of 2:1, solid content 45%, ethylene oxide mass content 14%, number average molecular weight 5000g / mol, functionality 3, hydroxyl value 21.0mgKOH / g;

[0106] Polyol 5: propylene glycol-based copolymer of ethylene oxide and propylene oxide, ethylene oxide content 40%, number average molecular weight 4000 g / mol, functionality 3, hydroxyl value 42.1 mgKOH / g;

[0107] Polyol 6: Propylene glycol-based copolymer of ethylene oxide and propylene oxide, 35% ethylene oxide content, number average molecular weight 4000 g / mol, functionality 2, hydroxyl value 28.1 mgKOH / g;

[0108] Polyol 7: propylene glycol-based copolymer of ethylene oxide and propylene oxide, ethylene oxide content 80%, number average molecular weight 4000 g / mol, functionality 3, hydroxyl value 42.1 mgKOH / g;

[0109] Specific preparation method of Isocynate 1-2 (calculate NCO mass fraction based on 1000g of final product)

[0110] Preparation of Isocynate 1: Add 550g of diphenylmethane diisocyanate (Wanhua Chemical, MDI-100) into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen tube, heat to 65°C, then add the calculated Polyol 1 50g, Polyol 6 120g, Polyol 3 80g, react at 80°C for 2h, cool to below 40°C, and then add 200g of carbodiimide modified isocyanate (Wanhua Chemical, CDMDI100L), the NCO mass fraction of Isocynate 1 is controlled at 24.0%;

[0111] Preparation of Isocynate 2: Add 100 g of diphenylmethane diisocyanate (Wanhua Chemical, MDI-100) into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen tube, heat to 65°C, then add the calculated Polyol 1 50 g, Polyol 6 120 g, and Polyol 3 80 g, react at 80°C for 2 hours, cool to below 40°C, and then add 200 g of carbodiimide modified isocyanate (Wanhua Chemical, CDMDI100L), 200 g of toluene diisocyanate (Wanhua Chemical, TDI-80), and 250 g of toluene diisocyanate trimer. The NCO mass fraction of Isocynate 2 is controlled at 24.0%.

[0112] Example 1

[0113] This embodiment provides a polyurethane foam material, the formulation of which is shown in Table 1. The polyurethane foam material is prepared by the following method:

[0114] At room temperature, the raw materials other than Isocynate 2 were placed in a reaction kettle, stirred for 15 minutes using a high-speed shear stirrer at a stirring speed of 3000 r / min, and then discharged. The discharged mixture was stirred with Isocynate 2 at 35° C. for 3 seconds, poured into a mold at 51° C., and the mold was opened in 6 minutes to obtain the polyurethane foam material.

[0115] Example 2

[0116] This embodiment provides a polyurethane foam material, the formulation of which is shown in Table 1. The polyurethane foam material is prepared by the following method:

[0117] At room temperature, the raw materials other than Isocynate 2 were placed in a reaction kettle, stirred for 10 minutes using a high-speed shear stirrer at a stirring speed of 2000 r / min, and then discharged. The discharged mixture was stirred with Isocynate 2 at 40° C. for 3 seconds, poured into a mold at 53° C., and the mold was opened in 6 minutes to obtain the polyurethane foam material.

[0118] Example 3

[0119] This embodiment provides a polyurethane foam material, the formulation of which is shown in Table 1. The polyurethane foam material is prepared by the following method:

[0120] At room temperature, the raw materials other than Isocynate 2 were placed in a reaction kettle, stirred for 20 minutes using a high-speed shear stirrer at a stirring speed of 4000 r / min, and then discharged. The discharged mixture was stirred with Isocynate 2 at 40° C. for 5 seconds, poured into a mold at 49° C., and the mold was opened in 4 minutes to obtain the polyurethane foam material.

[0121] Example 4

[0122] This embodiment provides a polyurethane foam material, the formulation of which is shown in Table 1. The polyurethane foam material is prepared by the following method:

[0123] At room temperature, the raw materials other than Isocynate 1 were placed in a reaction kettle, stirred for 15 minutes using a high-speed shear stirrer at a stirring speed of 3000 r / min, and then discharged. The discharged mixture was stirred with Isocynate 1 at 35° C. for 3 seconds, poured into a mold at 51° C., and the mold was opened in 6 minutes to obtain the polyurethane foam material.

[0124] Example 5

[0125] This embodiment provides a polyurethane foam material, the formulation of which is shown in Table 1. The polyurethane foam material is prepared by the following method:

[0126] At room temperature, the raw materials other than Isocynate 1 were placed in a reaction kettle, stirred for 20 minutes using a high-speed shear stirrer at a stirring speed of 2000 r / min, and then discharged. The discharged mixture at 40° C. was mixed and stirred with Isocynate 1 at 35° C., poured into a mold at 50° C., and the mold was opened in 6 minutes to obtain the polyurethane foam material.

[0127] Comparative Example 1

[0128] The difference between this comparative example and Example 1 is that Polyol 6 is replaced by Polyol 7 of equal mass, and the rest is the same as Example 1.

[0129] Table 1

[0130]

[0131]

[0132] Note: The units in Table 1 are in parts by weight.

[0133] Performance Testing

[0134] The polyurethane foam materials described in Examples 1-5 and Comparative Example 1 were tested as follows: (1) Density, kg / m 3 :According to ASTM D-792 standard;

[0135] (2) Hardness, ASKER C: according to ASTM D-2240;

[0136] (3) Ball rebound, %: according to ASTM D3574;

[0137] (4) Compression set, %: according to ASTM D-395-B;

[0138] (5) Tensile strength, MPa: in accordance with ASTM D-412 Die C; (6) Elongation at break, %: in accordance with ASTM D-412 Die C; (7) Tear strength, N / mm: in accordance with ASTM D-624 Die C. The test results are summarized in Table 2.

[0139] Table 2

[0140]

[0141]

[0142] According to the data in Table 2, the density of the polyurethane foam material of the present invention is between 140.6 and 300.2 kg / m 3 The ASKER C hardness is between 28-45, the ball rebound is above 29%, the compression permanent deformation is within 13.5%, the elongation at break is above 130.6%, and the tear strength is above 3.5%. The polyurethane foam material of the present invention has the characteristics of low density, high hardness, low compression permanent deformation and high ball rebound, and has excellent mechanical properties such as elongation at break and tear strength.

[0143] In the preferred technical solution (taking Examples 1-3 as examples), the density of the polyurethane foam material of the present invention is 140.6-190.5 kg / m 3 The ASKER C hardness is between 28-45, the ball rebound is above 44%, the compression permanent set is within 3.6%, the elongation at break is above 130.6%, and the tear strength is above 3.5%.

[0144] Analysis of Comparative Example 1 and Example 1 shows that the performance of Comparative Example 1 is not as good as that of Example 1, which proves that the performance of the obtained polyurethane foam material is better when three polyether polyols with ethylene oxide in a specific mass content range are used in combination.

[0145] Analysis of Example 4 and Example 1 shows that the performance of Example 4 is not as good as that of Example 1. Example 4 belongs to a traditional low-density polyurethane foam material, which proves that the modified isocyanate prepolymer includes toluene diisocyanate and / or toluene diisocyanate trimer, and the obtained polyurethane foam material has better performance.

[0146] Analysis of Example 5 and Example 1 shows that Example 5 is a high-density polyurethane foam material, and Examples 1-3 have elasticity comparable to that of high-density products while ensuring low density, proving that the polyurethane foam material obtained by including toluene diisocyanate and / or toluene diisocyanate trimer in the modified isocyanate prepolymer has better performance.

[0147] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A polyurethane foam material, characterized in that: The polyurethane foam material is obtained by reacting a polyether polyol composition and a modified isocyanate prepolymer; The polyether polyol composition comprises three different polyether polyols, wherein the mass content of ethylene oxide in the raw materials for preparing the three different polyether polyols is independently less than 50%; The polyether polyol composition comprises a first polyether polyol, a second polyether polyol and a third polyether polyol; The raw material for preparing the first polyether polyol includes 10%-20% by mass of ethylene oxide; The raw material for preparing the second polyether polyol includes 10%-20% by mass of ethylene oxide; The raw material for preparing the third polyether polyol includes ethylene oxide in an amount of 30% to 50% by mass, but not equal to 50% by mass; The modified isocyanate prepolymer comprises a first modified isocyanate prepolymer, a second modified isocyanate prepolymer and a third modified isocyanate prepolymer; The second modified isocyanate prepolymer includes toluene diisocyanate and / or toluene diisocyanate trimer; The average functionality of the first polyether polyol is 2-4; The number average molecular weight of the first polyether polyol is 2000-8000 g / mol; The hydroxyl value of the first polyether polyol is 14-112.2 mgKOH / g; The average functionality of the second polyether polyol is 2-4; The number average molecular weight of the second polyether polyol is 2000-8000 g / mol; The hydroxyl value of the second polyether polyol is 14-112.2 mgKOH / g; The average functionality of the third polyether polyol is 2-4; The number average molecular weight of the third polyether polyol is 1000-8000 g / mol; The hydroxyl value of the third polyether polyol is 14-112.2 mgKOH / g; The first modified isocyanate prepolymer includes urethane modified isocyanate; The third modified isocyanate prepolymer includes carbodiimide-modified isocyanate.

2. The polyurethane foam material according to claim 1, characterized in that The second polyether polyol is obtained by copolymerization and grafting modification of styrene and acrylonitrile.

3. The polyurethane foam material according to claim 1, characterized in that The solid content of the second polyether polyol is 20%-45%.

4. The polyurethane foam material according to claim 1, characterized in that: The polyether polyol composition further comprises an auxiliary agent.

5. The polyurethane foam material according to claim 4, characterized in that: The auxiliary agent includes any one of a foaming agent, a catalyst, a chain extender or a color paste, or a combination of at least two of them.

6. The polyurethane foam material according to claim 1, characterized in that: Based on the total mass of the polyether polyol composition being 100%, the mass percentage of the first polyether polyol is 40%-95%.

7. The polyurethane foam material according to claim 1, characterized in that: Based on the total mass of the polyether polyol composition being 100%, the mass percentage of the second polyether polyol is 5%-50%.

8. The polyurethane foam material according to claim 1, characterized in that: Based on the total mass of the polyether polyol composition being 100%, the mass percentage of the third polyether polyol is 0.5%-10%.

9. The polyurethane foam material according to claim 4, characterized in that: Taking the total mass of the polyether polyol composition as 100%, the mass percentage of the auxiliary agent is 0%-22%.

10. The polyurethane foam material according to claim 5, characterized in that: Based on the total mass of the polyether polyol composition being 100%, the mass percentage of the foaming agent is 1%-10%.

11. The polyurethane foam material according to claim 5, characterized in that: Based on the total mass of the polyether polyol composition being 100%, the mass percentage of the catalyst is 0.2%-2%.

12. The polyurethane foam material according to claim 5, characterized in that: Based on the total mass of the polyether polyol composition being 100%, the mass percentage of the chain extender is 0%-5%.

13. The polyurethane foam material according to claim 5, characterized in that: Taking the total mass of the polyether polyol composition as 100%, the mass percentage of the color paste is 0%-5%.

14. The polyurethane foam material according to claim 5, characterized in that: The foaming agent includes any one of water, liquid carbon dioxide, chlorofluorocarbon compounds or hydrochlorofluorocarbon compounds, or a combination of at least two thereof.

15. The polyurethane foam material according to claim 14, characterized in that Based on the total mass of the polyether polyol composition being 100%, the mass percentage of the water is 1.3%-2.5%.

16. The polyurethane foam material according to claim 5, characterized in that: The catalyst includes an amine catalyst.

17. The polyurethane foam material according to claim 16, characterized in that The amine catalyst includes any one of bis(dimethylaminoethyl) ether, triethylenediamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine or dimethylethanolamine, or a combination of at least two thereof.

18. The polyurethane foam material according to claim 5, characterized in that: The chain extender includes any one of methyl propylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol or 1,4-butanediol, or a combination of at least two thereof.

19. The polyurethane foam material according to claim 5, characterized in that: The color paste includes any one of red color paste, orange color paste, yellow color paste, green color paste, blue color paste, purple color paste or black color paste, or a combination of at least two of them.

20. The polyurethane foam material according to claim 1, characterized in that The mass ratio of the polyether polyol composition to the modified isocyanate prepolymer is 100:(40-80).

21. The polyurethane foam material according to claim 1, characterized in that In the modified isocyanate prepolymer, the mass percentage of isocyanate groups is 23%-32%.

22. The polyurethane foam material according to claim 1, characterized in that The urethane-modified isocyanate is obtained by reacting polyol and isocyanate.

23. The polyurethane foam material according to claim 22, characterized in that The average functionality of the polyol is 2-3.

24. The polyurethane foam material according to claim 22, characterized in that The polyols include a fourth polyether polyol, a fifth polyether polyol and a sixth polyether polyol.

25. The polyurethane foam material according to claim 24, characterized in that The average functionality of the fourth polyether polyol is 2-3.

26. The polyurethane foam material according to claim 24, characterized in that The number average molecular weight of the fourth polyether polyol is 1000-8000 g / mol.

27. The polyurethane foam material according to claim 24, characterized in that The hydroxyl value of the fourth polyether polyol is 14.0-224.4 mgKOH / g.

28. The polyurethane foam material according to claim 24, characterized in that The average functionality of the fifth polyether polyol is 2.

29. The polyurethane foam material according to claim 24, characterized in that The fifth polyether polyol has a number average molecular weight of 1000-10000 g / mol.

30. The polyurethane foam material according to claim 24, characterized in that The hydroxyl value of the fifth polyether polyol is 11.22-112.2 mgKOH / g.

31. The polyurethane foam material according to claim 24, characterized in that The average functionality of the sixth polyether polyol is 2.

32. The polyurethane foam material according to claim 24, characterized in that The number average molecular weight of the sixth polyether polyol is 1000-10000 g / mol.

33. The polyurethane foam material according to claim 24, characterized in that The hydroxyl value of the sixth polyether polyol is 11.22-112.2 mgKOH / g.

34. The polyurethane foam material according to claim 24, characterized in that The raw material for preparing the sixth polyether polyol includes propylene oxide.

35. The polyurethane foam material according to claim 24, characterized in that Based on the total mass of the polyol being 100%, the mass percentage of the fourth polyether polyol is 20%-80%.

36. The polyurethane foam material according to claim 24, characterized in that Based on the total mass of the polyol being 100%, the mass percentage of the fifth polyether polyol is 10%-70%.

37. The polyurethane foam material according to claim 24, characterized in that Based on the total mass of the polyol being 100%, the mass percentage of the sixth polyether polyol is 1%-10%.

38. The polyurethane foam material according to claim 1, characterized in that Based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the first modified isocyanate prepolymer is 30%-80%.

39. The polyurethane foam material according to claim 1, characterized in that Based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the second modified isocyanate prepolymer is 1%-70%.

40. The polyurethane foam material according to claim 1, characterized in that Based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the toluene diisocyanate is 10%-50%.

41. The polyurethane foam material according to claim 1, characterized in that Based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the toluene diisocyanate trimer is 1%-20%.

42. The polyurethane foam material according to claim 1, characterized in that Based on the total mass of the modified isocyanate prepolymer being 100%, the mass percentage of the third modified isocyanate prepolymer is 10%-30%.

43. A method for preparing the polyurethane foam material according to any one of claims 1 to 42, characterized in that: The preparation method comprises the following steps: The polyether polyol composition and the modified isocyanate prepolymer are mixed and reacted to obtain a polyurethane foam material.

44. The preparation method according to claim 43, characterized in that: The mixing temperature is 35-45°C.

45. The preparation method according to claim 43, characterized in that: The mixing time is 2-8s.

46. ​​The preparation method according to claim 43, characterized in that The temperature of the reaction is 45-55°C.

47. The preparation method according to claim 43, characterized in that The reaction time is 4-6 minutes.

48. The preparation method according to claim 43, characterized in that The preparation method of the polyether polyol composition comprises the following steps: mixing a first polyether polyol, a second polyether polyol and a third polyether polyol to obtain a polyether polyol composition.

49. The preparation method according to claim 48, characterized in that The mixed raw materials also include auxiliary agents.

50. The preparation method according to claim 48, characterized in that The mixing method includes stirring.

51. The preparation method according to claim 50, wherein the stirring speed is 3000-5000 r / min. The preparation method according to claim 50, wherein the stirring temperature is 10-50°C.

53. The preparation method according to claim 50, wherein the stirring time is 10-30 min.

54. The preparation method according to claim 43, characterized in that: The preparation method of the modified isocyanate prepolymer comprises the following steps: mixing polyol and isocyanate, reacting, and obtaining the modified isocyanate prepolymer.

55. The preparation method according to claim 54, characterized in that: The reaction is carried out under stirring.

56. The preparation method according to claim 55, characterized in that The stirring speed is 10-300 r / min.

57. The preparation method according to claim 54, characterized in that: The reaction temperature is 60-95°C.

58. The preparation method according to claim 54, characterized in that: The reaction time is 2-4h.

59. A shoe insole, characterized in that: The insole comprises the polyurethane foam material according to any one of claims 1-42.

60. The insole according to claim 59, characterized in that The insole comprises a poured insole.

Images