Soft polyurethane foam material and preparation method and application thereof

Abstract

The invention relates to a soft polyurethane foam material and a preparation method and application thereof, which mainly solves the problems in the prior art that the soft polyurethane foam has poor physical properties and low peeling strength with an insert, and the polyurethane system of a conventional polycarbonate polyol has a large viscosity, resulting in a limited addition amount and poor system fluidity. The invention adopts a soft polyurethane foam material, which is composed of components A and B in a weight ratio of 100:25-55. In terms of weight, component A includes 10-40 parts of polycarbonate polyol I, 40-90 parts of polyether polyol, and polymer polyol. 0-20 parts, 1-4 parts of foaming agent, 0.5-1.5 parts of cross-linking agent, 0.5-1.5 parts of catalyst, 0.4-1 part of foam stabilizer; component B includes 5.8-59.3 parts of polycarbonate polyol II and 100 parts of isocyanate monomer; polycarbonate polyols I and II are polymerized by CO2 and alkylene oxide, with functionality 2-4, molecular weight 1000-3000, CO2 content 7-30wt%, primary hydroxyl content 20-95wt%. The technical solution has better solved the above problems and can be used in industrial applications of blister seats.

Description

Technical Field

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

[0002] Polyurethane foam has the characteristics of low density, high comfort, and easy processing and molding. It is widely used in the automotive field, such as seats, armrests, ceilings, carpets and other systems. In polyurethane products, foam products with an appropriate amount of polycarbonate polyol are compared with ordinary polyether polyol products. Due to the increase in ester bond content, the molecular polarity increases accordingly, thus having higher adhesion properties, physical and mechanical properties, aging resistance and other advantages.

[0003] For product inserts with high surface energy such as armrest frames and blister seats, polyurethane foam is difficult to infiltrate, resulting in low peel strength between the polyurethane foam product and the frame. The general solutions are as follows: 1. Add coupling agent, but the cost is too high; 2. Add polyester to introduce ester bonds, but the solubility with the raw material system is poor, the system viscosity increases too high, and the flow performance becomes poor; therefore, it is of great practical significance to develop a polyurethane foam material system that contains ester bonds to improve foam performance and has good solubility and fluidity.

[0004] Chinese patent CN 109912768A discloses a method for preparing a polyether composition and a low-VOC polyurethane foam. The composition includes a polyether polyol and a polyether carbonate polyol having a primary hydroxyl molar content of ≥40 mol%, and is preheated and melted with a blowing agent, a chain extender, a catalyst, a cell opener and a foam stabilizer, mixed evenly, cooled, and then isocyanate is added to mix and polymerize to obtain a polyurethane foam; however, the viscosity of the polyether carbonate polyol is relatively high, the amount of polyether polycarbonate in the whole system is very limited, the degree of improvement of the mechanical properties is not high, and the viscosity of the system will increase and the fluidity will deteriorate.

[0005] Chinese patent CN105722880A discloses a mixture of polyether carbonate polyol and polyether polyol for manufacturing polyurethane flexible foam material, wherein polyurethane flexible foam is manufactured by reacting an isocyanate component with an isocyanate reactive component, wherein the isocyanate reactive component comprises a mixture of polyether carbonate polyol and polyether polyol as components, wherein the total amount of polyether carbonate polyol is 20 to 80 wt % and the total amount of polyether polyol is 20 to 80 wt % based on the total weight of the polyol present in the isocyanate reactive component; however, the amount of polyether polycarbonate in the reaction system is also limited, and the mechanical properties of the foam such as stretching and tearing are poor.

[0006] Chinese patent CN101535364A discloses a method for producing a flexible polyurethane foam, wherein the flexible polyurethane foam is produced by reacting a polyisocyanate with a compound having at least two hydrogen atoms reactive to an isocyanate group in the presence of a blowing agent, wherein the polyisocyanate comprises a functional group ≥ 2, a hydroxyl value of 10 to 500 mgKOH / g and CO 2 Polyether carbonate polyol with a content of ≥2wt%; however, the foam produced therefrom has low tensile strength and poor bonding properties. Summary of the invention

[0007] One of the technical problems to be solved by the present invention is that the soft polyurethane foam in the prior art has poor physical and mechanical properties and low peel strength with an insert, while the conventional polyurethane system containing polycarbonate polyol has a large viscosity, resulting in a limited addition amount and poor system fluidity. A soft polyurethane foam material is provided, which has the advantages of good physical and mechanical properties, high peel strength with an insert, low system viscosity and good fluidity.

[0008] The second technical problem to be solved by the present invention is to provide a method for preparing a soft polyurethane foam material corresponding to the first technical problem.

[0009] The third technical problem to be solved by the present invention is to provide an application of a soft polyurethane foam material corresponding to the first technical problem.

[0010] In order to solve one of the above technical problems, the technical solution provided by the present invention is as follows: a soft polyurethane foam material, composed of component A and component B, the weight ratio of component A to component B is 100:25-55, wherein component A comprises, by weight: 10-40 parts of polycarbonate polyol I, 40-90 parts of polyether polyol, 0-20 parts of polymer polyol, 1-4 parts of foaming agent, 0.5-1.5 parts of cross-linking agent, 0.5-1.5 parts of catalyst, and 0.4-1 part of foam stabilizer; component B is an isocyanate modified by polycarbonate polyol II, comprising, by weight, 5.8-59.3 parts of polycarbonate polyol II and 100 parts of isocyanate monomer; wherein the polycarbonate polyols I and II are both CO 2 It is polymerized with alkylene oxide, with a functionality of 2 to 4 and a molecular weight of 1000 to 3000. 2 The content is 7-30wt%, the primary hydroxyl content is 20-95wt%; the functionality of the polyether polyol is 2.5-4, the molecular weight is 6000-8500, and the primary hydroxyl content is 70-90wt%; the foaming agent is water; the cross-linking agent is selected from at least one of small molecule alcohols or alcohol amines; the catalyst is selected from at least one of amine catalysts; the foam stabilizer is selected from at least one of polyether modified silicone surfactants.

[0011] In the above technical scheme, preferably, the isocyanate modified by polycarbonate polyol II is formed by carbamate modification of polycarbonate polyol II and isocyanate monomer, and its isocyanate group content is 20-31.5wt%; the isocyanate monomer is selected from at least one of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate or carbodiimide modified isocyanate.

[0012] In the above technical solution, preferably, the polycarbonate polyols I and II are both made of CO 2 It is polymerized with propylene oxide.

[0013] In the above technical solution, preferably, the functionality of the polycarbonate polyol I is 2 to 4, the molecular weight is 1000 to 3000, 2 The content is 15-20wt%, and the primary hydroxyl content is 85-95wt%.

[0014] In the above technical solution, preferably, the functionality of the polycarbonate polyol II is 2 to 2.7, the molecular weight is 2300 to 3000, and the CO 2 The content is 20-30wt%, and the primary hydroxyl content is 50-60wt%.

[0015] In the above technical scheme, preferably, the cross-linking agent is selected from at least one of glycerol, diethylene glycol, diethanolamine, triethanolamine or triisopropanolamine; the catalyst is selected from at least one of triethylenediamine, bis(dimethylaminoethyl) ether, tetramethylethylenediamine, tetramethylpropylenediamine, pentamethyldiethylenetriamine or pentamethyldipropylenetriamine; the foam stabilizer is selected from at least one of B-8715, B-8734, B-8738, B-8747 or B-8745.

[0016] To solve the second technical problem above, the present invention provides the following technical solution: a method for preparing a soft polyurethane foam material, comprising the following steps:

[0017] (1) In container A, add 10-40 parts of polycarbonate polyol I, 40-90 parts of polyether polyol, 0-20 parts of polymer polyol, 1-4 parts of foaming agent, 0.5-1.5 parts of cross-linking agent, 0.5-1.5 parts of catalyst, and 0.4-1 parts of foam stabilizer, by weight, and mix thoroughly to obtain component A; wherein the polycarbonate polyol I is composed of CO 2 It is polymerized with alkylene oxide, with a functionality of 2 to 4 and a molecular weight of 1000 to 3000. 2The content is 7-30wt%, the primary hydroxyl content is 20-95wt%; the functionality of the polyether polyol is 2.5-4, the molecular weight is 6000-8500, and the primary hydroxyl content is 70-90wt%; the foaming agent is water; the cross-linking agent is selected from at least one of small molecule alcohols or alcohol amines; the catalyst is selected from at least one of amine catalysts; the foam stabilizer is selected from at least one of polyether modified silicone surfactants;

[0018] (2) Add 100 parts by weight of isocyanate monomer to reaction vessel B, raise the temperature to 60° C., add 5.8 to 59.3 parts of polycarbonate polyol II half an hour later, raise the temperature to 80° C., and react for 2 hours to obtain component B having an isocyanate group content of 20 to 31.5 wt %; wherein the polycarbonate polyol II is composed of CO 2 It is polymerized with alkylene oxide, with a functionality of 2 to 4 and a molecular weight of 1000 to 3000. 2 The content is 7 to 30 wt%, and the primary hydroxyl content is 20 to 95 wt%;

[0019] (3) The temperature of components A and B is controlled at 23±2°C, and the mass ratio of component A to component B is 100:25-55. Component A is poured into container C, and then component B is poured into container C containing component A. A disperser with a rotation speed of 2500-3500 rpm is used for dispersion and stirring for 3-10 seconds. The mixture is poured into a mold at a temperature of 40-60°C and taken out after 1.5-3 minutes to obtain a soft polyurethane foam material.

[0020] In the above technical solution, preferably, the polycarbonate polyols I and II are both made of CO 2 It is polymerized with propylene oxide.

[0021] In the above technical solution, preferably, the functionality of the polycarbonate polyol I is 2 to 4, the molecular weight is 1000 to 3000, 2 The content is 15-20wt%, and the primary hydroxyl content is 85-95wt%.

[0022] In the above technical solution, preferably, the functionality of the polycarbonate polyol II is 2 to 2.7, the molecular weight is 2300 to 3000, and the CO 2 The content is 20-30wt%, and the primary hydroxyl content is 50-60wt%.

[0023] In the above technical scheme, preferably, the isocyanate monomer is selected from at least one of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate or carbodiimide modified isocyanate; the cross-linking agent is selected from at least one of propylene glycol, diethylene glycol, diethanolamine, triethanolamine or triisopropanolamine.

[0024] In the above technical solution, preferably, the catalyst is selected from at least one of triethylenediamine, bis(dimethylaminoethyl) ether, tetramethylethylenediamine, tetramethylpropylenediamine, pentamethyldiethylenetriamine or pentamethyldipropylenetriamine.

[0025] In the above technical solution, preferably, the foam stabilizer is selected from at least one of B-8715, B-8734, B-8738, B-8747 or B-8745.

[0026] In order to solve the third of the above technical problems, the technical solution provided by the present invention is as follows: the prepared soft polyurethane foam material is used in the industrial application of blister seats.

[0027] The soft polyurethane foam material of the present invention adds polycarbonate polyol to the component A of the polyurethane foaming system, and modifies isocyanate with polycarbonate polyol in the component B, and cooperates with the polyether polyol, polymer polyol, foaming agent, crosslinking agent, catalyst and foam stabilizer in the system, thereby increasing the content of polar groups in the system, improving the peel strength between the soft polyurethane foam and the insert, especially the high surface energy insert, which can be as high as 4.6N / mm. Due to the increase in the polarity of the soft segment, the physical properties of the soft polyurethane foam are improved, such as tensile strength up to 339kPa, elongation at break up to 189%, and tear strength up to 6.03N / cm. On the other hand, the use of high CO 2 The content of polycarbonate polyol with a large molecular weight is modified with isocyanate monomer by urethane, which also increases the CO content in the system. 2 content, reduces the viscosity of the system, the flow circumference can reach 74.2cm, and the fluidity is good; therefore, the soft polyurethane foam material of the present invention has the advantages of good physical and mechanical properties, high peel strength and good fluidity, and achieves good technical effects.

[0028] The performance index testing method of the soft polyurethane foam material prepared by the present invention is as follows:

[0029] Fluidity evaluation: Using the fluidity evaluation mold in Chinese utility model patent CN202023181312.7, pour 100g of the molded foam formula into the reaction tank at 45°C and mature for 2 minutes. Open the mold and take out the annular sample. Measure the length of the annular sample to obtain the flow circumference to evaluate the fluidity. The longer the flow circumference, the better the fluidity.

[0030] Apparent density (kg / m 3 ): ISO 845-2006;

[0031] Tensile strength (kPa): GB / T 6344-2008;

[0032] Elongation at break (%): GB / T 6344-2008;

[0033] Tear strength (N / cm): GB / T 10808-2006;

[0034] Peel strength (N / mm): GB / T 2792-2014.

[0035] The present invention will be further described below by way of examples, but are not limited thereto. DETAILED DESCRIPTION

[0036] Table 1 List of raw materials

[0037]

[0038] [Example 1]

[0039] A method for preparing a soft polyurethane foam material comprises the following steps:

[0040] (1) In container A, add 10 parts of polycarbonate polyol D, 90 parts of polyether polyol A, 2 parts of blowing agent water, 1 part of crosslinking agent diethylene glycol, 0.2 parts of catalyst bis(dimethylaminoethyl ether), 0.4 parts of catalyst triethylenediamine, 0.4 parts of foam stabilizer B-8715, and 0.2 parts of foam stabilizer B-8734, by weight, and mix thoroughly to obtain component A;

[0041] (2) In reaction vessel B, 50 parts of Lupranate MS, 25 parts of Lupranate MIPS, and 25 parts of Cosmonate LL were added, and the temperature was raised to 60° C. After half an hour, 22 parts of polycarbonate polyol A were added, and the temperature was raised to 80° C. and reacted for 2 hours to obtain component B with an NCO mass percentage of 26%;

[0042] (3) The temperature of components A and B was controlled at 23°C, the mass ratio of component A / component B was 100 / 40, component A was poured into container C according to the measurement, and component B was poured into container C containing component A according to the measurement, stirred at a speed of 3000 rpm for 5 seconds, poured into a mold at a temperature of 40°C, and taken out after 2.5 minutes to obtain a soft polyurethane foam material product. Its performance data is shown in Table 3.

[0043] [Examples 2 to 6]

[0044] Examples 2 to 6 are carried out according to the steps in Example 1, except that the reaction raw materials and raw material ratios are different, as shown in Table 2; the performance index data of the prepared soft polyurethane foam material are shown in Table 3.

[0045] Table 2 Mass fractions of each component of the soft polyurethane foam material in Examples 1 to 6 and Comparative Examples 1 to 2

[0046]

[0047]

[0048] [Comparative Example 1]

[0049] Comparative Example 1 was carried out according to the steps of Example 1, except that the types of reaction raw materials and the raw material ratios were different, as shown in Table 2. The performance index data of the prepared soft polyurethane foam material are shown in Table 3.

[0050] [Comparative Example 2]

[0051] Comparative Example 2 is carried out according to steps (1) and (3) of Example 1. No reaction is required in step (2). The components are directly mixed and stirred according to the mass fractions of Table 2. The types of reaction raw materials and the raw material ratios are shown in Table 2. The performance index data of the prepared soft polyurethane foam material are shown in Table 3.

[0052] Table 3 Performance data of soft polyurethane foam materials in Examples 1 to 6 and Comparative Examples 1 to 2

[0053]

[0054]

[0055] As shown in Table 3, in Examples 1 to 6, in addition to modifying the isocyanate with polycarbonate polyol in component B, polycarbonate polyol is also added to component A of the polyurethane foaming system, which increases the content of polar groups in the system and improves the peel strength between the soft polyurethane foam and the insert, especially the high surface energy insert, which is as high as 4.6 N / mm. At the same time, due to the increase in the polarity of the soft segment, the physical properties of the soft polyurethane foam are also improved, with a tensile strength of up to 339 kPa, an elongation at break of up to 189%, and a tear strength of up to 6.03 N / cm. In Examples 1 to 6, in addition to modifying the isocyanate with polycarbonate polyol in component B, polycarbonate polyol is also added to component A of the polyurethane foaming system, which increases the content of polar groups in the system and improves the peel strength between the soft polyurethane foam and the insert, especially the high surface energy insert, which is as high as 4.6 N / mm. At the same time, due to the increase in the polarity of the soft segment, the physical properties of the soft polyurethane foam are also improved, with a tensile strength of up to 339 kPa, an elongation at break of up to 189%, and a tear strength of up to 6.03 N / cm. 2 The polycarbonate polyol with high molecular weight and high content is modified with isocyanate monomer to reduce the viscosity of the system and increase the CO content in the system. 2 The content is high, the flow circumference can reach 74.2cm, the fluidity is good, and at the same time the physical and mechanical properties such as tensile strength, elongation at break, tear strength, etc. are improved, and the peel strength also reaches more than 4.0N / mm.

[0056] Therefore, the soft polyurethane foam material prepared by the present invention has the advantages of good physical and mechanical properties, high peel strength and good fluidity, achieves good technical effects, and can be used in the industrial application of blister seats.

Claims

1. A soft polyurethane foam material, consisting of component A and component B, wherein the weight ratio of component A to component B is 100:25-55, wherein: Component A includes, by weight: 10-40 parts of polycarbonate polyol I, 40-90 parts of polyether polyol, 0-20 parts of polymer polyol, 1-4 parts of foaming agent, 0.5-1.5 parts of crosslinking agent, 0.5-1.5 parts of catalyst, and 0.4-1 parts of foam stabilizer; Component B is an isocyanate modified by polycarbonate polyol II, and by weight includes 5.8-59.3 parts of polycarbonate polyol II and 100 parts of isocyanate monomer; the functionality of the polyether polyol is 2. 5~4, a molecular weight of 6000~8500, and a primary hydroxyl content of 70~90wt%; the foaming agent is water; the isocyanate modified by polycarbonate polyol II is prepared by urethane modification of polycarbonate polyol II and isocyanate monomer, and its isocyanate content is 20~31.5wt%; the isocyanate monomer is selected from 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane At least one of diisocyanate or carbodiimide modified isocyanate; the polycarbonate polyols I and II are both polymerized by CO2 and alkylene oxide; the functionality of the polycarbonate polyol I is 2-4, the molecular weight is 1000-3000, the CO2 content is 15-20wt%, and the primary hydroxyl content is 85-95wt%; the functionality of the polycarbonate polyol II is 2-2.7, the molecular weight is 2300-3000, the CO2 content is 20-30wt%, the primary hydroxyl content is 85-95wt%. The hydroxyl content is 50-60wt%; the cross-linking agent is selected from at least one of glycerol, diethylene glycol, diethanolamine, triethanolamine or triisopropanolamine; the catalyst is selected from at least one of triethylenediamine, bis(dimethylaminoethyl) ether, tetramethylethylenediamine, tetramethylpropylenediamine, pentamethyldiethylenetriamine or pentamethyldipropylenetriamine; the foam stabilizer is selected from at least one of B-8715, B-8734, B-8738, B-8747 or B-8745.

2. A method for preparing the soft polyurethane foam material according to claim 1, comprising the following steps: (1) In container A, add 10-40 parts of polycarbonate polyol I, 40-90 parts of polyether polyol, 0-20 parts of polymer polyol, 1-4 parts of foaming agent, 0.5-1.5 parts of cross-linking agent, 0.5-1.5 parts of catalyst and 0.4-1 parts of foam stabilizer, by weight, and mix thoroughly to obtain component A; wherein the polycarbonate polyol I is prepared by polymerization of CO2 and alkylene oxide; the functionality of the polycarbonate polyol I is 2-4, the molecular weight is 1000-3000, the CO2 content is 15-20wt%, and the primary hydroxyl content is 85-95wt%; the foaming agent is 0.5-1.5 parts of cross-linking agent, 0.5-1.5 parts of catalyst and 0.4-1 parts of foam stabilizer, and mix thoroughly to obtain component A; The crosslinking agent is water; the functionality of the polyether polyol is 2.5-4, the molecular weight is 6000-8500, and the primary hydroxyl content is 70-90wt%; the crosslinking agent is selected from at least one of glycerol, diethylene glycol, diethanolamine, triethanolamine or triisopropanolamine; the catalyst is selected from at least one of triethylenediamine, bis(dimethylaminoethyl) ether, tetramethylethylenediamine, tetramethylpropylenediamine, pentamethyldiethylenetriamine or pentamethyldipropylenetriamine; the foam stabilizer is selected from at least one of B-8715, B-8734, B-8738, B-8747 or B-8745; (2) Add 100 parts by weight of isocyanate monomer to reaction vessel B, raise the temperature to 60°C, add 5.8-59.3 parts of polycarbonate polyol II half an hour later, raise the temperature to 80°C, and react for 2 hours to obtain component B with an isocyanate group content of 20-31.5wt%; wherein the polycarbonate polyol II is prepared by polymerization of CO2 and alkylene oxide, and the functionality of the polycarbonate polyol II is 2-2.7, the molecular weight is 2300-3000, the CO2 content is 20-30wt%, and the primary hydroxyl content is 50-60wt%; the isocyanate monomer is selected from at least one of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate or carbodiimide modified isocyanate; (3) The temperature of components A and B is controlled at 23±2°C. The mass ratio of component A to component B is 100:25~55. Component A is poured into container C, and then component B is poured into container C containing component A. The mixture is dispersed and stirred for 3~10 seconds using a disperser at a speed of 2500~3500 rpm. The mixture is poured into a mold at a temperature of 40~60°C and taken out after 1.5~3 minutes to obtain a soft polyurethane foam material.

3. Use of the soft polyurethane foam material according to claim 1 in a blister seat.

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