Polyurethane foam as well as preparation method and application thereof

Abstract

The invention relates to the technical field of foam materials, in particular to polyurethane foam and a preparation method and application thereof. The polyurethane foam is prepared from the following raw materials in parts by weight: 90 to 110 parts of active polyester polyol, 55 to 75 parts of dicarbamate modified isocyanate and 0.3 to 1.0 part of an active fiber adsorbent, wherein the active polyester polyol comprises at least three hydroxyl groups, and the functionality of the active polyester polyol is greater than 3; the raw materials of the polyurethane foam can reduce the residue of amine substances in the polyurethane foam so as to reduce the odor of the polyurethane foam, and the active fiber adsorbent can effectively reduce the content of volatile organic compounds in the polyurethane foam. In addition, by selecting the catalyst, the far end of the cavity of the mold is fully filled with the foaming material, and the low-odor polyurethane foam with uniform foam holes and excellent NVH performance is obtained.

Description

Technical Field

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

[0002] The sound insulation pads and carpets used in the front of the passenger compartment of the car interior are generally required to have sound absorption and insulation performance and environmental friendliness. In order to achieve good sound absorption and insulation performance, the material of the sound insulation pad is generally a combination of a hard layer and a soft layer. The hard layer mainly plays a sound insulation role, and the soft layer mainly plays a sound absorption role. The soft layer plays a key role in the sound absorption and insulation of the parts. When selecting materials, it is generally required that the material is porous and can fit well with the sheet metal. At present, one of the commonly used materials for the soft layer is polyurethane foam.

[0003] At present, the main preparation process of polyurethane foam for automobile sound insulation pads is the closed mold foaming process. Traditional polyurethane soft foam has a high odor, and polyurethane materials will produce a large amount of volatile organic compounds (VOC) during the closed mold foaming process. At the same time, this type of automobile sound insulation pad parts often have the disadvantages of complex structure and varying thickness. Due to the production requirements of sound insulation pads, it is necessary to improve the fluidity, filling and environmental friendliness of the foaming formula of polyurethane materials. However, the requirements for improving fluidity and filling will undoubtedly further increase the odor and VOC content of polyurethane.

[0004] At present, the polyurethane materials related to automobiles include: (1) polyurethane materials using acid-terminated catalysts. The acid-terminated catalysts do not catalyze at the first time, which improves the fluidity of the polyurethane material formula, so that the "end" shape of the polyurethane product can be quickly filled. When the acid-terminated catalyst is affected by the mold temperature and the acid-terminated catalyst is released, it will quickly start and solidify to complete the foaming reaction, playing a role of rapid filling and foaming; (2) using rapeseed oil to prepare rigid polyurethane foam materials, which mainly solves the problem that the existing rigid polyurethane foam plastics rely on petroleum as raw materials, and instead uses vegetable oil for deep processing to synthesize bio-based polyols, thereby preparing rigid polyurethane foam; (3) using 5-chloromethyl salicylaldehyde as a raw material, and then reacting with quaternary ammonium salts of hydroxy tertiary amines and diprimary amines to prepare polyols containing quaternary ammonium cations and Salen functional groups in the molecular structure, and then using the polyols to prepare functional polyurethanes; (4) using high-functionality polyether polyols and high-viscosity modified polymethylene polyphenyl polyisocyanates to prepare polyurethane foams, the density of which is greater than 60kg / m 3 , and it also has the advantage of ultra-low temperature resistance, so it can be used for pipeline insulation. Summary of the invention

[0005] The present application provides a polyurethane foam and a preparation method and application thereof to solve the following technical problems: how to reduce the odor and volatile organic compound content of polyurethane, and the problems of uneven foaming and poor tearing resistance when molding complex and irregular large parts.

[0006] In a first aspect, the present application provides a polyurethane foam, including a catalyst, a crosslinking agent, an additive and a foaming agent, wherein the raw materials of the polyurethane foam include, by weight: 90 to 110 parts of active polyester polyol, 55 to 75 parts of diurethane modified isocyanate and 0.3 to 1.0 parts of active fiber adsorbent;

[0007] Wherein, the active polyester polyol includes at least 3 hydroxyl groups, and the functionality of the active polyester polyol is greater than 3.

[0008] Optionally, the raw materials of the active polyester polyol include polyol and organic dibasic acid; wherein the polyol includes at least two of the following:

[0009] Ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, neopentyl glycol, 1,4-butanediol and polyhydric alcohols;

[0010] The organic dibasic acid includes an aliphatic dibasic acid and / or an aromatic dibasic acid.

[0011] Optionally, the polyhydric alcohol includes pentaerythritol, and the number of hydroxyl functional groups of the polyhydric alcohol is greater than 4.

[0012] Optionally, the raw materials of the polyurethane foam further include, by weight:

[0013] Stabilizer: 1.5 to 2.0 parts, catalyst: 0.4 to 1.5 parts, cross-linking agent: 0.5 to 1.5 parts, additive: 0.5 to 2 parts and foaming agent: 4 to 7 parts.

[0014] Optionally, the catalyst comprises at least one of the following:

[0015] A diol solution of modified bis(dimethylaminoethyl) ether, an organic tin catalyst, an organic bismuth catalyst and a pentamethyldiethylenetriamine quaternary ammonium salt.

[0016] Optionally, the catalyst includes a mixture of a diol solution of modified bisdimethylaminoethyl ether, an organic tin catalyst, an organic bismuth catalyst and a quaternary ammonium salt of pentamethyldiethylenetriamine; the molar ratio of the diol solution of modified bisdimethylaminoethyl ether, the organic tin, the organic bismuth and the quaternary ammonium salt of pentamethyldiethylenetriamine is 1-2:3-4:2-3:2-4.

[0017] Optionally, the stabilizer includes methylhydroxy silicone oil and / or polyoxypropylene modified silicone oil; and / or,

[0018] The crosslinking agent comprises an aqueous solution of a polyacid ester; and / or,

[0019] The additive comprises modified butanediol and / or modified ethylene glycol; and / or,

[0020] The blowing agent includes water.

[0021] In a second aspect, the present application provides a method for preparing the polyurethane foam according to the first aspect, the method comprising:

[0022] Preparation of reactive polyester polyols;

[0023] The active polyester polyol, stabilizer, catalyst, cross-linking agent, active fiber adsorbent, additive and foaming agent are mixed to obtain a combined polyester polyol mixture;

[0024] The diurethane modified isocyanate and the combined polyester polyol mixture are mixed and then foamed to obtain polyurethane foam.

[0025] Optionally, the mixing includes adding materials for mixing at a preset feeding flow rate, wherein the preset feeding flow rate is 80 L / min to 110 L / min; and / or,

[0026] The pressure of the foaming molding is 11Mpa-20Mpa, and the temperature of the foaming molding is 35°C-50°C.

[0027] In a third aspect, the present application provides an application of a polyurethane foam, wherein the application comprises using the polyurethane foam described in the first aspect or the polyurethane foam prepared by the method described in the second aspect to prepare an automobile sound insulation material.

[0028] The above technical solution provided by the embodiment of the present application has the following advantages compared with the prior art:

[0029] A polyurethane foam provided in an embodiment of the present application includes a catalyst, a cross-linking agent, an additive and a foaming agent. The raw materials of the polyurethane foam include, by weight: 90 to 110 parts of an active polyester polyol, 55 to 75 parts of a diurethane modified isocyanate and 0.3 to 1.0 parts of an active fiber adsorbent; wherein the active polyester polyol includes at least 3 hydroxyl groups, and the functionality of the active polyester polyol is greater than 3. The reactive polyester polyol may include at least 3 hydroxyl groups, and the functionality of the reactive polyester polyol is greater than 3, which can promote the hydroxyl groups of the reactive polyester polyol and the isocyanate groups of the diurethane modified isocyanate to fully react chemically, so as to avoid the isocyanate groups of the diurethane modified isocyanate from generating free amine substances in the polyurethane foam, thereby reducing the residual amine substances in the polyurethane foam, and further reducing the generation of odor, so that the foam has a lower odor. In addition, the porous structure and high specific surface area of ​​the reactive fiber can absorb the volatile organic small molecules generated by the reactive polyester polyol and the diurethane modified isocyanate in the chemical reaction, thereby reducing the content of volatile organic compounds in the polyurethane foam, and further effectively reducing the odor of the polyurethane foam and the content of volatile organic compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the present application.

[0031] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0032] Figure 1 A schematic diagram of a polyurethane foam product provided in an embodiment of the present application;

[0033] Figure 2 A schematic flow chart of a method for preparing polyurethane foam provided in an embodiment of the present application. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0035] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be understood as a rigid limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within the range; for example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which applies regardless of the range; in addition, whenever a numerical range is indicated in this document, it is meant to include any cited numbers (fractions or integers) within the indicated range.

[0036] In this document, the terms including "including" and "including" mean "including but not limited to". Relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. "And / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone; where A and B can be singular or plural. "At least one" means one or more, and "plurality" means two or more; "at least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items; for example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple. Unless otherwise specified, various raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.

[0037] It should be noted that, with respect to the prior art (1) of the background technology, the inventors found that the polyurethane foam prepared by this technology mainly improves its odor and VOC content by selecting raw materials, but cannot improve the by-products of the reaction process and avoid the influence of unreacted free monomers. In addition, the effect of this technology on improving the odor and VOC content of polyurethane foam is limited; with respect to the prior art (2) of the background technology, the inventors found that this technology is mainly used for the preparation of hard foam, and is not suitable for closed-mold soft foam, and does not mention the improvement of NVH performance and odor; with respect to the prior art (3) of the background technology, the inventors found that this technology is mainly used for polyurethane films, multifunctional polyurethane-based gas purification materials, etc., and is not suitable for foaming polyurethane materials. In addition, this technology cannot improve the odor and VOC content of polyurethane materials; with respect to the prior art (4) of the background technology, the inventors found that the polyurethane material prepared by this technology is not suitable for automobile passenger compartment front wall sound insulation pad products, and does not mention the improvement effect and control method of polyurethane materials in terms of odor and VOC.

[0038] Figure 1 A schematic diagram of a polyurethane foam product provided in an embodiment of the present application is exemplarily shown;

[0039] like Figure 1 As shown, the embodiment of the present application provides a polyurethane foam, including a catalyst, a cross-linking agent, an additive and a foaming agent. The raw materials of the polyurethane foam include, by weight: 90 to 110 parts of active polyester polyol, 55 to 75 parts of diurethane modified isocyanate and 0.3 to 1.0 parts of active fiber adsorbent;

[0040] Wherein, the active polyester polyol comprises at least 3 hydroxyl groups, and the functionality of the active polyester polyol is greater than 3;

[0041] In these embodiments, the weight fraction of the active polyester polyol can be 90 to 110 parts, and the weight fraction of the dicarbamate-modified isocyanate can be 55 to 75 parts, which can promote the hydroxyl group of the active polyester polyol and the isocyanate group of the dicarbamate-modified isocyanate to fully react chemically, so as to avoid the isocyanate group of the dicarbamate-modified isocyanate to generate free amine substances in the polyurethane foam, thereby reducing the residual amine substances in the polyurethane foam, and further reducing the generation of odor, so that the foam has a lower odor; the mass fraction of the active fiber adsorbent can be 0.3 to 1.0 parts, which can adsorb the volatile organic small molecules generated by the active polyester polyol and the dicarbamate-modified isocyanate in the chemical reaction, thereby reducing the content of volatile organic compounds in the polyurethane foam.

[0042] It should be noted that the activated carbon fiber can have a specific surface area of ​​≥2000m2 / g and short fiber materials with a porosity ≥ 90%.

[0043] It should be noted that the molecular weight of the reactive polyester polyol is 4500-5500.

[0044] In some optional embodiments, the raw materials of the reactive polyester polyol include polyol and organic dibasic acid; wherein the polyol includes at least two of the following:

[0045] Ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, neopentyl glycol, 1,4-butanediol and polyhydric alcohols;

[0046] The organic dibasic acid includes an aliphatic dibasic acid and / or an aromatic dibasic acid;

[0047] In these embodiments, the raw materials of the active polyester polyol may include polyols and organic dibasic acids, and the polyols may include at least two of ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, neopentyl glycol, 1,4-butanediol and polyhydric alcohols, and the organic dibasic acids may include aliphatic dibasic acids and / or aromatic dibasic acids, which can further promote the hydroxyl groups of the active polyester polyol and the isocyanate groups of the diurethane-modified isocyanate to fully react chemically, so as to avoid the isocyanate groups of the diurethane-modified isocyanate to generate free amine substances in the polyurethane foam, thereby further reducing the residual amine substances in the polyurethane foam and making it have a lower odor.

[0048] In some optional embodiments, the polyol comprises a polyhydric alcohol, and the number of hydroxyl functional groups of the polyhydric alcohol is greater than 4;

[0049] In these embodiments, the polyol may include a polyhydric alcohol, and the number of hydroxyl functional groups of the polyhydric alcohol may be greater than 4, which can cause the polyol to have a sufficient number of hydroxyl groups. A sufficient number of hydroxyl groups can cause the reactive polyester polyol to fully react chemically with the diurethane-modified isocyanate, so as to avoid the isocyanate group of the diurethane-modified isocyanate from generating free amine substances in the polyurethane foam, thereby further reducing the residual amine substances in the polyurethane foam and making the polyurethane foam have a lower odor.

[0050] In some optional embodiments, the raw materials of the polyurethane foam further include, by weight:

[0051] Stabilizer: 1.5 to 2.0 parts, catalyst: 0.4 to 1.5 parts, cross-linking agent: 0.5 to 1.5 parts, additive: 0.5 to 2 parts and foaming agent: 4 to 7 parts;

[0052] In these embodiments, the weight proportion of the stabilizer can be 1.5 to 2.0 parts, the weight proportion of the catalyst can be 0.4 to 1.5 parts, the weight proportion of the cross-linking agent can be 0.5 to 1.5 parts, the weight proportion of the additive can be 0.5 to 2 parts, and the weight proportion of the foaming agent can be 4 to 7 parts, which can promote the active polyester polyol to fully react chemically with the diurethane modified isocyanate to avoid the isocyanate group of the diurethane modified isocyanate to generate free amine substances in the polyurethane foam, thereby reducing the odor of the polyurethane foam. In addition, these reagents can promote the chemical reaction to proceed fully, so as to obtain a polyurethane foam with sufficient elasticity.

[0053] In some optional embodiments, the catalyst comprises at least one of the following:

[0054] A diol solution of modified bis(dimethylaminoethyl)ether, an organic tin catalyst, an organic bismuth catalyst and a quaternary ammonium salt of pentamethyldiethylenetriamine;

[0055] In these embodiments, the catalyst may include at least one of a diol solution of modified bis(dimethylaminoethyl)ether, an organic tin catalyst, an organic bismuth catalyst, and a pentamethyldiethylenetriamine quaternary ammonium salt. The catalyst may be used to delay the foaming time of the foaming agent, thereby improving the dispersion of the raw materials of the polyurethane foam, and further obtaining a uniformly foamed polyurethane foam.

[0056] In some optional embodiments, the catalyst comprises a mixture of a diol solution of modified bisdimethylaminoethyl ether, an organic tin catalyst, an organic bismuth catalyst and a pentamethyldiethylenetriamine quaternary ammonium salt; the molar ratio of the diol solution of modified bisdimethylaminoethyl ether, the stannous octoate catalyst, the organic bismuth catalyst and the pentamethyldiethylenetriamine quaternary ammonium salt is (1-2):(3-4):(2-3):(2-4);

[0057] In these embodiments, the catalyst may include a mixture of a diol solution of modified bisdimethylaminoethyl ether, an organic tin catalyst, an organic bismuth catalyst and a pentamethyldiethylenetriamine quaternary ammonium salt, and the molar ratio of the diol solution of modified bisdimethylaminoethyl ether, the organic tin catalyst, the organic bismuth catalyst and the pentamethyldiethylenetriamine quaternary ammonium salt may be 1-2:3-4:2-3:2-4. The pentamethyldiethylenetriamine quaternary ammonium salt and the organic tin catalyst may be used to improve the fluidity of the polyurethane foam raw material, thereby obtaining a uniformly foamed polyurethane foam. In addition, the organic bismuth catalyst and the diol solution of modified bisdimethylaminoethyl ether may delay foaming, so that the foaming material is fully filled to the far end of the injection port to avoid a violent chemical reaction, thereby making the pore size of the polyurethane foam more uniform, and further giving the polyurethane foam a higher elastic property.

[0058] The molar ratio of the diol solution of the modified bisdimethylaminoethyl ether, the organotin catalyst, the organobismuth catalyst and the pentamethyldiethylenetriamine quaternary ammonium salt can be 1:3:2:2, 1:3:2:3, 1:3:2:4, 1:3:3:2, 1:3:3:3, 1:3:3:4, 1:4:2:2, 1:4:3:3, 1:4:3:4, 2:3:2:2, 2:3:2:3, 2:3:2:4, 2:3:3:2, 2:3:3:3, 2:3:3:4, 2:4:2:2, 2:4:2:3, 2:4:2:4, 2:4:3:2, 2:4:3:3 or 2:4:3:4.

[0059] In some optional embodiments, the stabilizer includes methylhydroxy silicone oil and / or polyoxypropylene modified silicone oil; and / or,

[0060] The crosslinking agent comprises an aqueous solution of a polyacid ester; and / or,

[0061] The additive comprises modified butanediol and / or modified ethylene glycol; and / or,

[0062] The blowing agent includes water;

[0063] In these embodiments, the stabilizer may include methylhydroxy silicone oil and / or polyoxypropylene modified silicone oil. These stabilizers may act as surfactants used in the foaming of polyurethane foam, and may effectively reduce the surface tension of the polyurethane foam system, thereby forming more nucleation points in the polyurethane foam; in addition, these nucleation sites may be combined with polyurea, a product of the chemical reaction process of active polyester polyol and diurethane modified isocyanate, thereby promoting these nucleation sites to be uniformly attached to the inner wall of the pore structure of the polyurethane foam. The nucleation sites attached to the inner wall of the pore structure may control the uniformity of the opening degree of the corresponding pore structure, thereby obtaining a polyurethane foam product having a uniform and fine foam pore structure through the stabilizer.

[0064] In addition, the crosslinking agent may include an aqueous solution of a polyacid ester, and the additive may include modified butanediol and / or modified ethylene glycol, and the foaming agent may include water, which can promote the full molding of the polyurethane foam to obtain a porous polyurethane foam product with uniform voids.

[0065] Figure 2 A schematic flow chart of a method for preparing polyurethane foam provided in an embodiment of the present application is shown exemplarily;

[0066] Based on a general inventive concept, such as Figure 2 As shown, the embodiment of the present application provides a method for preparing the polyurethane foam, the method comprising:

[0067] S1. Preparation of reactive polyester polyols;

[0068] S2. The active polyester polyol, stabilizer, catalyst, crosslinking agent, active fiber adsorbent, additives and blowing agent are mixed to obtain a combined polyester polyol mixture;

[0069] S3. The diurethane-modified isocyanate and the combined polyester polyol mixture are mixed, and then foamed to obtain a polyurethane foam.

[0070] This method is a method for preparing the above-mentioned polyurethane foam. The specific composition of the polyurethane foam can refer to the above-mentioned embodiment. Since this method adopts part or all of the technical solutions of the above-mentioned embodiment, it at least has all the beneficial effects brought by the technical solutions of the above-mentioned embodiment, which will not be repeated here one by one.

[0071] It should be noted that the active polyester polyol, stabilizer, catalyst, cross-linking agent, active fiber adsorbent, additive and foaming agent can be mixed by stirring at room temperature, and the stirring time can be 50 minutes.

[0072] It should be noted that the diurethane-modified isocyanate and the combined polyester polyol mixture can be mixed using a high-pressure gun tip.

[0073] It should be noted that the preparation process of the active polyester polyol is to prepare the polyol and the organic dibasic acid through esterification and polycondensation reaction.

[0074] In some optional embodiments, the mixing includes adding and mixing at a preset feeding flow rate, wherein the preset feeding flow rate is 80 L / min to 110 L / min; and / or,

[0075] The foaming pressure is 11Mpa to 20Mpa, and the foaming temperature is 35°C to 50°C;

[0076] In these embodiments, mixing may include adding and mixing at a preset feeding flow rate, and the preset feeding flow rate may be 80L / min to 110L / min, which may promote the preliminary mixing of the active polyester polyol, stabilizer, catalyst, cross-linking agent, active fiber adsorbent, additive and foaming agent in the feeding stage, thereby obtaining a uniformly distributed combined polyester polyol mixture; in addition, the foaming molding pressure may be 11Mpa to 20Mpa, and the foaming molding temperature may be 35°C to 50°C, which may promote sufficient chemical reaction between the diurethane-modified isocyanate and the active polyester polyol to obtain a polyurethane foam product having a uniform and fine foam pore structure.

[0077] The preset feed flow rate can be 80 L / min, 85 L / min, 90 L / min, 95 L / min, 100 L / min, 105 L / min or 110 L / min.

[0078] The foam molding pressure can be 11 MPa, 12 MPa, 13 MPa, 14 MPa, 15 MPa, 16 MPa, 17 MPa, 18 MPa, 19 MPa or 20 MPa.

[0079] The temperature of the foaming molding can be 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C.

[0080] It should be noted that the foaming is carried out in a closed mold.

[0081] Based on a general inventive concept, an embodiment of the present application provides an application of a polyurethane foam, wherein the application includes using the polyurethane foam or the polyurethane foam prepared by the method to prepare an automobile sound insulation material.

[0082] The application is realized based on the above method or polyurethane foam. The specific steps of the method or the specific composition of the polyurethane foam can refer to the above embodiment. Since the application adopts part or all of the technical solutions of the above embodiment, it has at least all the beneficial effects brought by the technical solutions of the above embodiment, which will not be described one by one here.

[0083] The present application is further described below in conjunction with specific examples. The experimental methods in the following examples that do not specify specific conditions are usually measured according to industry standards; if there are no corresponding industry standards, they are carried out according to common international standards, conventional conditions, or conditions recommended by the manufacturer.

[0084] Example 1

[0085] A polyurethane foam, wherein the raw materials of the polyurethane foam include, by weight: 100 parts of active polyester polyol, 55 parts of diurethane modified isocyanate, 0.5 parts of active fiber adsorbent, 1.5 parts of stabilizer, 0.5 parts of catalyst, 1.0 parts of crosslinking agent, 0.5 parts of additive and 5 parts of foaming agent;

[0086] Among them, the molecular weight of the active polyester polyol is 5000;

[0087] The activated fiber adsorbent is an activated carbon fiber adsorbent.

[0088] The raw materials of the active polyester polyol include polyol and organic dibasic acid; wherein the polyol is a mixture of ethylene glycol, diethylene glycol, trimethylolpropane, 1,4-butanediol and polyhydric alcohol; the molar ratio of ethylene glycol, diethylene glycol, trimethylolpropane, 1,4-butanediol and polyhydric alcohol is 2:2:1:1:4.

[0089] The organic dibasic acid is an aliphatic dibasic acid.

[0090] The polyhydric alcohol is pentaerythritol.

[0091] The catalyst comprises a mixture of a diol solution of modified bisdimethylaminoethyl ether, stannous octoate, bismuth oxide and pentamethyldiethylenetriamine quaternary ammonium salt; the molar ratio of the diol solution of modified bisdimethylaminoethyl ether, stannous octoate, organic bismuth and pentamethyldiethylenetriamine quaternary ammonium salt is 2:4:2:2.

[0092] The stabilizer includes a mixture of methylhydroxy silicone oil and polyoxypropylene modified silicone oil, and the mass ratio of the methylhydroxy silicone oil to the polyoxypropylene modified silicone oil is 3:1;

[0093] The crosslinking agent is an aqueous solution of polyacrylate;

[0094] The additive is a mixture of modified butanediol and modified ethylene glycol, and the mass ratio of the modified butanediol to the modified ethylene glycol is 1:1;

[0095] The blowing agent is water.

[0096] like Figure 2 As shown, the present application embodiment provides a method for preparing polyurethane foam, the method comprising:

[0097] S1. Preparation of reactive polyester polyols;

[0098] S2. The active polyester polyol, stabilizer, catalyst, crosslinking agent, active fiber adsorbent, additives and blowing agent are mixed to obtain a combined polyester polyol mixture;

[0099] S3. The diurethane-modified isocyanate and the combined polyester polyol mixture are mixed and then foamed to obtain polyurethane foam.

[0100] The mixing includes adding materials at a preset feeding flow rate for mixing, and the preset feeding flow rate is 90L / min;

[0101] The pressure of the foaming molding was 15 MPa, and the temperature of the foaming molding was 40°C.

[0102] Example 2

[0103] Based on the contents disclosed in Example 1, the following operations are further performed:

[0104] The raw materials of the polyurethane foam include, by weight: 100 parts of active polyester polyol, 65 parts of diurethane modified isocyanate, 0.7 parts of active fiber adsorbent, 0.5 parts of stabilizer, 1.0 parts of catalyst, 1.5 parts of crosslinking agent, 1.5 parts of additives and 6 parts of foaming agent;

[0105] Among them, the molecular weight of the active polyester polyol is 4500.

[0106] The raw materials of the active polyester polyol include polyol and organic dibasic acid; wherein the polyol is a mixture of ethylene glycol, trimethylolpropane, neopentyl glycol and polyhydric alcohol; the molar ratio of ethylene glycol, trimethylolpropane, neopentyl glycol and polyhydric alcohol is 2:3:1:4;

[0107] The organic dibasic acid is an aliphatic dibasic acid.

[0108] The polyhydric alcohol is a mixture of pentaerythritol and polyester triol, the molar ratio of pentaerythritol to polyester triol is 1:3, and the number of hydroxyl functional groups of the polyhydric alcohol is greater than 4.

[0109] The catalyst comprises a mixture of a diol solution of modified bisdimethylaminoethyl ether, stannous octoate, bismuth oxide and pentamethyldiethylenetriamine quaternary ammonium salt; the molar ratio of the diol solution of modified bisdimethylaminoethyl ether, stannous octoate, organic bismuth and pentamethyldiethylenetriamine quaternary ammonium salt is 1:3:3:3.

[0110] The stabilizer includes a mixture of methylhydroxy silicone oil and polyoxypropylene modified silicone oil, and the mass ratio of the methylhydroxy silicone oil to the polyoxypropylene modified silicone oil is 2:1;

[0111] The crosslinking agent is an aqueous solution of polyacrylate;

[0112] The additive is a mixture of modified butanediol and modified ethylene glycol, and the mass ratio of the modified butanediol to the modified ethylene glycol is 2:1;

[0113] The blowing agent is water.

[0114] The preset feed flow rate is 90L / min;

[0115] The pressure of the foaming molding was 13 MPa, and the temperature of the foaming molding was 45°C.

[0116] Example 3

[0117] Based on the contents disclosed in Example 1, the following operations are further performed:

[0118] The raw materials of the polyurethane foam include, by weight: 100 parts of active polyester polyol, 75 parts of diurethane modified isocyanate, 1.0 parts of active fiber adsorbent, 0.5 parts of stabilizer, 1.5 parts of catalyst, 1.0 parts of crosslinking agent, 2 parts of additives and 7 parts of foaming agent;

[0119] The active polyester polyol is a mixture of aromatic dicarboxylic acid-modified adipic acid polyester polyol and polycarbonate polyol, and the molecular weights are 4000 and 5500 respectively.

[0120] The raw materials of the active polyester polyol include polyol and organic dibasic acid; wherein the polyol is a mixture of ethylene glycol, trimethylolpropane, neopentyl glycol and polyhydric alcohol; the molar ratio of ethylene glycol, trimethylolpropane, neopentyl glycol and polyhydric alcohol is 2:3:1:4;

[0121] The organic dibasic acid is an aliphatic dibasic acid.

[0122] The polyhydric alcohol is a polyester triol.

[0123] The catalyst comprises a mixture of a diol solution of modified bisdimethylaminoethyl ether, stannous octoate, bismuth oxide and pentamethyldiethylenetriamine quaternary ammonium salt; the molar ratio of the diol solution of modified bisdimethylaminoethyl ether, stannous octoate, bismuth oxide and pentamethyldiethylenetriamine quaternary ammonium salt is 2:4:4.

[0124] The stabilizer includes a mixture of methylhydroxy silicone oil and polyoxypropylene modified silicone oil, and the mass ratio of the methylhydroxy silicone oil to the polyoxypropylene modified silicone oil is 1:1;

[0125] The crosslinking agent is an aqueous solution of polyacrylate;

[0126] The additive is a mixture of modified butanediol and modified ethylene glycol, and the mass ratio of the modified butanediol to the modified ethylene glycol is 1:1;

[0127] The blowing agent is water.

[0128] The preset feed flow rate is 90L / min;

[0129] The pressure of the foaming molding was 15 MPa, and the temperature of the foaming molding was 45°C.

[0130] Comparative Example 1

[0131] Based on the contents disclosed in Example 1, the following operations are further performed:

[0132] The raw materials of the polyurethane foam include, by weight: 100 parts of polyester polyol, 75 parts of toluene diisocyanate, 0.5 parts of stabilizer, 1.5 parts of catalyst, 1.0 parts of cross-linking agent, 2 parts of additives and 7 parts of foaming agent.

[0133] Polyester polyols are polyalkylene glycols;

[0134] The catalyst includes a mixture of triethylenediamine and pentamethyldiethylenetriamine; the molar ratio of triethylenediamine to pentamethyldiethylenetriamine is 5:4.

[0135] The stabilizer is silicone oil;

[0136] The crosslinking agent is an aqueous solution of polyacrylate;

[0137] The additive is a mixture of modified butanediol and modified ethylene glycol, and the mass ratio of the modified butanediol to the modified ethylene glycol is 1:1;

[0138] The blowing agent is water.

[0139] The preset feed flow rate is 90L / min;

[0140] The pressure of the foaming molding was 15 MPa, and the temperature of the foaming molding was 45°C.

[0141] Comparative Example 2

[0142] Based on the contents disclosed in Example 1, the following operations are further performed:

[0143] The raw materials of the polyurethane foam include, by weight: 90 parts of active polyester polyol, 45 parts of diurethane modified isocyanate, 0.5 parts of stabilizer, 1.5 parts of catalyst, 1.0 parts of crosslinking agent, 2 parts of additives and 7 parts of foaming agent;

[0144] The active polyester polyol is a mixture of aromatic dicarboxylic acid-modified adipic acid polyester polyol and polycarbonate polyol, and the molecular weights are 4000 and 5500 respectively.

[0145] The raw materials of the active polyester polyol include polyol and organic dibasic acid; wherein the polyol is a mixture of ethylene glycol, trimethylolpropane, neopentyl glycol and polyhydric alcohol; the molar ratio of ethylene glycol, trimethylolpropane, neopentyl glycol and polyhydric alcohol is 2:3:1:4;

[0146] The organic dibasic acids include aliphatic dibasic acids.

[0147] Polyhydric alcohols include polyester triols.

[0148] The catalyst includes a mixture of triethylenediamine and pentamethyldiethylenetriamine; the molar ratio of triethylenediamine to pentamethyldiethylenetriamine is 5:4.

[0149] The stabilizer includes a mixture of methylhydroxy silicone oil and polyoxypropylene modified silicone oil, and the mass ratio of the methylhydroxy silicone oil to the polyoxypropylene modified silicone oil is 1:1;

[0150] The crosslinking agent is an aqueous solution of polyacrylate;

[0151] The additive is a mixture of modified butanediol and modified ethylene glycol, and the mass ratio of the modified butanediol to the modified ethylene glycol is 1:1;

[0152] The blowing agent is water.

[0153] The preset feed flow rate is 90L / min;

[0154] The pressure of the foaming molding was 13 MPa, and the temperature of the foaming molding was 40°C.

[0155] Comparative Example 3

[0156] Based on the contents disclosed in Example 1, the following operations are further performed:

[0157] The raw materials of the polyurethane foam include, by weight: 70 parts of active polyester polyol, 50 parts of diurethane modified isocyanate, 0.5 parts of stabilizer, 0.5 parts of catalyst, 1.0 parts of crosslinking agent, 2 parts of additives and 7 parts of foaming agent;

[0158] The active polyester polyol is a mixture of aromatic dicarboxylic acid-modified adipic acid polyester polyol and polycarbonate polyol, and the molecular weights are 4000 and 5500 respectively.

[0159] The raw materials of the active polyester polyol include polyol and organic dibasic acid; wherein the polyol is a mixture of ethylene glycol, trimethylolpropane, neopentyl glycol and polyhydric alcohol; the molar ratio of ethylene glycol, trimethylolpropane, neopentyl glycol and polyhydric alcohol is 2:3:1:4;

[0160] The organic dibasic acid is an aliphatic dibasic acid.

[0161] The polyhydric alcohol is a mixture of polyester triol and pentaerythritol, and the molar ratio of pentaerythritol to polyester triol is 1:3.

[0162] The catalyst includes a mixture of triethylenediamine and pentamethyldiethylenetriamine; the molar ratio of triethylenediamine to pentamethyldiethylenetriamine is 4:3.

[0163] The stabilizer includes a mixture of methylhydroxy silicone oil and polyoxypropylene modified silicone oil, and the mass ratio of the methylhydroxy silicone oil to the polyoxypropylene modified silicone oil is 1:1;

[0164] The crosslinking agent is an aqueous solution of polyacrylate;

[0165] The additive is a mixture of modified butanediol and modified ethylene glycol, and the mass ratio of the modified butanediol to the modified ethylene glycol is 1:1;

[0166] The blowing agent is water.

[0167] The preset feed flow rate is 90L / min;

[0168] The pressure of the foaming molding was 15 MPa, and the temperature of the foaming molding was 45°C.

[0169] Related experiments and effect data:

[0170] The odor and VOC content of the polyurethane foam obtained in each embodiment and comparative example were analyzed, and the results are shown in Table 1.

[0171] Table 1 Odor and VOC content data of polyurethane foam obtained in various examples and comparative examples

[0172]

[0173]

[0174] As can be seen from Table 1, the polyurethane foam provided in the embodiment of the present application has a VOC content better than that of the polyurethane foam obtained in the comparative example, and can significantly reduce the volatility of amines in the polyurethane foam, which is beneficial to reducing the irritating amine odor of the polyurethane foam.

[0175] The polyurethane foams obtained in various embodiments were statistically analyzed for performance testing, and the results are shown in Table 2.

[0176] Table 2 Polyurethane foam performance data obtained from each embodiment

[0177]

[0178] It can be seen from Table 2 that the polyurethane foam provided in the embodiment of the present application has better material fluidity, higher tear strength and better resilience than the polyurethane foam obtained in the comparative example, and the polyurethane foam obtained in the embodiment has the best indicators.

[0179] In summary, the polyurethane foam provided in the embodiment of the present application can promote the hydroxyl group of the active polyester polyol and the isocyanate group of the diurethane modified isocyanate to fully react chemically, so as to avoid the isocyanate group of the diurethane modified isocyanate from generating free amine substances in the polyurethane foam, thereby reducing the residual amine substances in the polyurethane foam. The polyurethane foam with reduced amine content has lower odor. In addition, the active fiber adsorbent can adsorb the volatile organic small molecules generated in the chemical reaction of the active polyester polyol and the diurethane modified isocyanate, thereby reducing the content of volatile organic compounds in the polyurethane foam. Further, the odor and the content of volatile organic compounds in the polyurethane foam can be effectively reduced by the active polyester polyol, the diurethane modified isocyanate and the active fiber adsorbent.

[0180] Furthermore, in a polyurethane foam provided in an embodiment of the present application, an activated carbon fiber adsorbent is added into the polyurethane foam, and the large specific surface area and a large number of microporous structures of the activated carbon fiber adsorbent can be fully utilized to adsorb residual small molecule products and free monomers in the polyurethane foam. In addition, since the pore size of the activated carbon fiber adsorbent is small and it is monodisperse, the activated carbon fiber adsorbent can increase the gravitational force of the gas molecules entering the micropores of the polyurethane foam radiating inward from the pore wall, thereby promoting the extremely strong adsorption force of the activated carbon fiber adsorbent, and further can greatly improve the odor and VOC content of the polyurethane foam.

[0181] In addition, a polyurethane foam provided in an embodiment of the present application also uses an active polyester polyol having more than three active hydroxyl groups, which can enable the active polyester polyol to have a sufficient amount of hydroxyl groups. The sufficient amount of hydroxyl groups can quickly react with the isocyanate groups of the diurethane-modified isocyanate, thereby improving the reaction efficiency and reducing the residual amount of isocyanate groups, thereby effectively reducing the odor of the polyurethane foam.

[0182] In addition, the polyurethane foam provided in the embodiment of the present application can be applied to sound insulation products used in passenger compartments of various types of vehicles, such as sound insulation pads, sound insulation walls, etc.

[0183] The above is only a specific implementation of the present application, so that those skilled in the art can understand or implement the present application. It will be apparent to those skilled in the art that various modifications to these embodiments are possible, and the general principles defined in the present application can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown in the present application, but will conform to the widest scope consistent with the principles and novel features applied for by the present application.

Claims

1. A polyurethane foam comprising a catalyst, a crosslinking agent, an additive and a blowing agent, characterized in that: The raw materials of the polyurethane foam include, by weight: 90 to 110 parts of active polyester polyol, 55 to 75 parts of diurethane modified isocyanate and 0.3 to 1.0 parts of active fiber adsorbent; Wherein, the active polyester polyol includes at least 3 hydroxyl groups, and the functionality of the active polyester polyol is greater than 3.

2. The polyurethane foam according to claim 1, characterized in that The raw materials of the active polyester polyol include polyol and organic dibasic acid; wherein the polyol includes at least two of the following: Ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol and 1,4-butanediol and polyhydric alcohols; The organic dibasic acid includes an aliphatic dibasic acid or an aromatic dibasic acid.

3. The polyurethane foam according to claim 2, characterized in that The polyol includes a polyhydric alcohol, and the number of hydroxyl functional groups of the polyhydric alcohol is ≥4.

4. The polyurethane foam according to claim 1, characterized in that The raw materials of the polyurethane foam further include, by weight: Stabilizer: 1.5 to 2.0 parts, catalyst: 0.4 to 1.5 parts, cross-linking agent: 0.5 to 1.5 parts, additive: 0.5 to 2 parts and foaming agent: 4 to 7 parts.

5. The polyurethane foam according to claim 4, characterized in that The catalyst comprises at least one of the following: A diol solution of modified bis(dimethylaminoethyl) ether, an organic tin catalyst, an organic bismuth catalyst and a pentamethyldiethylenetriamine quaternary ammonium salt.

6. The polyurethane foam according to claim 5, characterized in that The catalyst comprises a mixture of a diol solution of modified bisdimethylaminoethyl ether, an organic tin catalyst, an organic bismuth catalyst and a pentamethyldiethylenetriamine quaternary ammonium salt; the molar ratio of the diol solution of modified bisdimethylaminoethyl ether, the organic tin, the organic bismuth and the pentamethyldiethylenetriamine quaternary ammonium salt is 1-2:3-4:2-3:2-4.

7. The polyurethane foam according to claim 4, characterized in that The stabilizer includes methylhydroxy silicone oil or polyoxypropylene modified silicone oil; and / or, The crosslinking agent comprises an aqueous solution of a polyacid ester; and / or, The additive comprises modified butanediol and / or modified ethylene glycol; and / or, The blowing agent includes water.

8. A method for preparing the polyurethane foam according to any one of claims 1 to 7, characterized in that: The method comprises: Preparation of reactive polyester polyols; The active polyester polyol, stabilizer, catalyst, cross-linking agent, active fiber adsorbent, additive and foaming agent are mixed to obtain a combined polyester polyol mixture; The diurethane modified isocyanate and the combined polyester polyol mixture are mixed and then foamed to obtain polyurethane foam.

9. The method according to claim 7, characterized in that: The mixing includes adding materials at a preset feeding flow rate for mixing, wherein the preset feeding flow rate is 80L / min to 110L / min; and / or, The pressure of the foaming molding is 11Mpa-20Mpa, and the temperature of the foaming molding is 35°C-50°C.

10. An application of polyurethane foam, characterized in that: The application includes using the polyurethane foam according to any one of claims 1 to 7 or the polyurethane foam prepared by the method according to claim 8 or 9 to prepare automobile sound insulation materials.

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