Polyurethane foaming catalyst and preparation method, polyurethane sponge

Abstract

The present invention belongs to the technical field of polyurethane foaming, and specifically relates to a polyurethane foaming catalyst, a preparation method, and a polyurethane sponge. The polyurethane foaming catalyst comprises a main catalyst and a co-catalyst in a mass ratio of (6-8):1; the main catalyst comprises 3-dimethylaminopropyl urea and dimethylaminopropylamine diisopropyl alcohol; and the co-catalyst comprises bisdimethylaminopropylamine isopropyl alcohol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether. The polyurethane foam prepared using the catalyst has low odor, low content of volatile harmful compounds, high rebound rate, low cell collapse rate, and good antistatic properties.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane foaming, and particularly relates to a polyurethane foaming catalyst and a preparation method thereof, and a polyurethane sponge. Background Art

[0002] Polyurethane foam materials have the advantages of being lightweight, heat-insulating, resilient, and breathable, and have broad application prospects in the automotive field. For example, polyurethane soft foam can be used as car seat cushions, backrests, headrests, and decorative strips, while polyurethane rigid foam can be used as door panel linings, sun visors, and ceiling linings.

[0003] In recent years, as people's requirements for automobile quality and environmental protection continue to increase, the requirements for polyurethane foam materials are also getting higher and higher, especially the odor and VOC content of polyurethane foam materials are becoming more and more concerned.

[0004] The raw materials of polyurethane foam materials usually include polyether polyols, polymer polyols, isocyanates, catalysts, etc. The sources of their odor and VOC are mainly the volatile monomers remaining in polyether polyols and polymer polyols. In addition, tertiary amine catalysts are commonly used in polyurethane foam materials. Although the amount used in polyurethane foam materials is very small, they do not participate in the reaction. After the reaction is completed, they will remain in the porous structure of the polyurethane foam material. Their volatility will cause the polyurethane foam material to have a strong odor and high VOC content.

[0005] In the prior art, low-volatility tertiary amine catalysts are often used to reduce the odor and VOC content of polyurethane foam materials. For example, Chinese Patent Publication No. CN109485820A discloses a low-odor, low-VOC polyurethane high-resilience foam. Suitable low-volatility tertiary amine catalysts include Evonik (formerly American Gas Company)'s NE series non-emissive catalysts such as NE300 and NE1070, Momentive's EF series products such as EF602, EF608, EF150, and EF680, Huntsman's ZR-50 and DPA, and similar products sold by other companies on the market. Chinese patent publication number CN116789925A discloses a formaldehyde-free, low-odor polyurethane foam material and a preparation method thereof. The low-odor catalyst is a mixture of a reactive catalyst, an odorless, low-volatile equilibrium catalyst, and a delayed amine catalyst. The reactive catalyst includes at least one of N,N,N-trimethyl-N-hydroxyethyl bisaminoethyl ether (JEFFCAT ZF-10) and tetramethyldipropylenetriamine (TMBPA), the odorless, low-volatile equilibrium catalyst includes at least one of NA-702 and NA-720, and the delayed amine catalyst includes at least one of C-225 and A400.

[0006] However, the above technical solutions all require the use of specific polyols, aldehyde cleaning agents and low-odor catalysts to achieve an odor level of 3.5. Summary of the Invention

[0007] The present invention aims to address one or more technical problems existing in the aforementioned prior art and to provide at least a beneficial alternative. Specifically, the present invention provides a polyurethane foaming catalyst, a preparation method, and a polyurethane sponge. The polyurethane foam produced using this catalyst exhibits low odor, low levels of volatile harmful compounds, high rebound rate, low cell collapse rate, and good antistatic properties.

[0008] On the one hand, the present invention provides a catalyst for polyurethane foaming, which is composed of a main catalyst and a co-catalyst in a mass ratio of (6-8):1; the main catalyst is 3-dimethylaminopropyl urea and dimethylaminopropylamine diisopropyl alcohol; the co-catalyst is bisdimethylaminopropylamine isopropyl alcohol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether.

[0009] The CAS number of 3-dimethylaminopropyl urea is: 31506-43-1.

[0010] The CAS number of dimethylaminopropylamine diisopropyl alcohol is: 63469-23-8.

[0011] The CAS number of bis(dimethylaminopropyl)aminoisopropyl alcohol is 67151-63-7.

[0012] The CAS number of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether is: 83016-70-0.

[0013] Optionally, the mass ratio of the 3-dimethylaminopropyl urea to dimethylaminopropylamine diisopropyl alcohol is (1.2-1.6):1.

[0014] Optionally, the mass ratio of the bis(dimethylaminopropyl)amine isopropyl alcohol to N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether is (1.1-1.3):1.

[0015] On the other hand, the present invention provides a method for preparing the above-mentioned polyurethane foaming catalyst, comprising the following steps: uniformly mixing 3-dimethylaminopropyl urea, dimethylaminopropylamine diisopropyl alcohol, bisdimethylaminopropylamine isopropyl alcohol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether to obtain the catalyst.

[0016] On the other hand, the present invention provides a polyurethane sponge, comprising component A and component B; the component A, calculated by mass, comprises 100 parts of polyether polyol, 10-20 parts of organosilicon-modified nano-scale conductive titanium dioxide, 2-5 parts of foaming agent, 0.5-2 parts of foam stabilizer, and 0.3-0.5 parts of the above-mentioned polyurethane foaming catalyst; the component B is isocyanate.

[0017] Optionally, the polyether polyol has a hydroxyl value of 30-70 mgKOH / g.

[0018] Optionally, the organosilicon is selected from at least one of 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride and 3-(trimethoxysilyl)propyldimethylhexadecylammonium chloride.

[0019] Optionally, the particle size of the nano-scale conductive titanium dioxide is 50-250 nm.

[0020] Optionally, the preparation method of the organosilicon-modified nano-scale conductive titanium dioxide is as follows: nano-scale conductive titanium dioxide, organosilicon and water are mixed, stirred, washed and dried.

[0021] Optionally, the mass ratio of the nano-scale conductive titanium dioxide, organic silicon and water is (1.5-2):1:(15-20).

[0022] Optionally, the stirring conditions are: a rotation speed of 200-400 rpm, a temperature of 40-60° C., and a time of 6-10 h.

[0023] Optionally, the foaming agent is selected from at least one of water, cyclopentane and n-pentane.

[0024] Optionally, the foam stabilizer comprises cyclic siloxane and polyether epoxy co-modified silicone oil in a mass ratio of (0.3-0.5):10.

[0025] Optionally, the cyclic siloxane is selected from at least one of 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

[0026] Optionally, the polyether epoxy co-modified silicone oil is selected from at least one of DY-ETE301 polyether epoxy co-modified silicone oil, DY-ETE302G-2 polyether epoxy co-modified silicone oil, DY-ETE302G2-T polyether epoxy co-modified silicone oil and DY-ETE301H polyether epoxy co-modified silicone oil produced by Shandong Dayi Chemical Co., Ltd.

[0027] Optionally, the isocyanate is selected from at least one of diphenylmethylene diisocyanate and toluene diisocyanate.

[0028] Optionally, the mass ratio of the polyether polyol to the isocyanate is 100:(30-60).

[0029] Optionally, the method for preparing the polyurethane sponge comprises the following steps: stirring and mixing the raw materials in component A uniformly, adding component B, and stirring uniformly to obtain a mixture; placing the mixture in a foaming mold and ripening to obtain the mixture.

[0030] Optionally, the aging temperature is 60° C., and the aging time is 2-4 minutes.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. The present invention uses 3-dimethylaminopropyl urea and dimethylaminopropylamine diisopropyl alcohol as main catalysts and is compounded with co-catalysts (bisdimethylaminopropylamine isopropyl alcohol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether). The odor level of the prepared polyurethane foam can reach level 2, and the odor level can reach level 3 after being placed at 65°C for 2 hours. In addition, the polyurethane foam has a low content of volatile harmful compounds without the need for specific polyether polyols and aldehyde cleaning agents.

[0033] 2. The present invention adopts organic silicon modified nano-scale conductive titanium dioxide and specific foam stabilizer (cyclic siloxane and polyether epoxy co-modified silicone oil) to work together to make the polyurethane sponge have excellent antistatic properties (surface resistance of 10 6 Ω / sq) while avoiding the decline in the resilience of the polyurethane sponge (the rebound rate can reach more than 70%) and the increase in the cell collapse rate (the cell collapse rate is below 5%). BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0035] Figure 1 This is a physical picture of the polyurethane sponge prepared in Application Example 1 of the present invention.

[0036] Figure 2 This is a physical picture of the polyurethane sponge prepared in Comparative Application Example 4 of the present invention.

[0037] Figure 3 This is a physical picture of the polyurethane sponge with collapsed cells prepared in Comparative Application Example 6 of the present invention. DETAILED DESCRIPTION

[0038] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0039] In a first aspect, an embodiment of the present invention provides a catalyst for polyurethane foaming, which is composed of a main catalyst and a co-catalyst in a mass ratio of (6-8):1; the main catalyst is 3-dimethylaminopropyl urea and dimethylaminopropylamine diisopropyl alcohol; the co-catalyst is bisdimethylaminopropylamine isopropyl alcohol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether.

[0040] There are dozens or even hundreds of types of catalysts known in the art for polyurethane foaming, but not all catalysts can produce polyurethane foam with low odor. In order to reduce the curing temperature and odor after polyurethane foaming, the inventors unexpectedly discovered during experiments that using 3-dimethylaminopropyl urea and dimethylaminopropylamine diisopropyl alcohol as the main catalyst in combination with co-catalysts (bisdimethylaminopropylamine isopropyl alcohol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether) can balance the foaming and gelling reactions while combining with isocyanate, reducing catalyst volatilization. The resulting polyurethane foam has an odor level of 2 and an odor level of 3 after being stored at 65°C for 2 hours. In addition, the polyurethane foam has a low content of volatile harmful compounds without the need for specific polyether polyols and aldehyde cleaning agents.

[0041] In some embodiments, the mass ratio of the main catalyst to the co-catalyst can be 6:1, 7:1, 8:1, or a range consisting of any two thereof.

[0042] In some embodiments, the mass ratio of 3-dimethylaminopropyl urea to dimethylaminopropylamine diisopropyl alcohol is (1.2-1.6):1.

[0043] In some embodiments, the mass ratio of the bis(dimethylaminopropyl)amine isopropanol to N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether is (1.1-1.3):1.

[0044] The preferred catalyst of the present invention needs to strictly control the mass ratio of the main catalyst and the co-catalyst as well as the mass ratio of 3-dimethylaminopropyl urea and dimethylaminopropylamine diisopropyl alcohol, otherwise it will cause the odor of the polyurethane foam to become stronger and also affect the resilience and cell collapse rate of the polyurethane foam.

[0045] In some embodiments, the mass ratio of 3-dimethylaminopropyl urea to dimethylaminopropylamine diisopropyl alcohol can be 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, or a range consisting of any two thereof.

[0046] In some embodiments, the 3-dimethylaminopropyl urea is selected from at least one of Dingxin DXCAT@NE1070 and Evonik DABCO@NE1070.

[0047] In some embodiments, the dimethylaminopropylamine diisopropyl alcohol is selected from at least one of Dingxin DXCAT@DPA, Huntsman JEFFCAT@DPA, and Evonik DABCO@NE1050.

[0048] In some embodiments, the mass ratio of the bis(dimethylamino)propylamine isopropanol to N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether can be 1.1:1, 1.2:1, 1.3:1, or a range consisting of any two thereof.

[0049] In some embodiments, the bis(dimethylaminopropyl)aminoisopropyl alcohol is selected from at least one of Dingxin DXCAT@ZR50 and Huntsman JEFFCAT@ZR50.

[0050] In some embodiments, the N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether is Evonik DABCO@NE-310.

[0051] On the other hand, the present invention provides a method for preparing the above-mentioned polyurethane foaming catalyst, comprising the following steps: uniformly mixing 3-dimethylaminopropyl urea, dimethylaminopropylamine diisopropyl alcohol, bisdimethylaminopropylamine isopropyl alcohol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether to obtain the catalyst.

[0052] On the other hand, the present invention provides a polyurethane sponge, comprising component A and component B; the component A, calculated by mass, comprises 100 parts of polyether polyol, 10-20 parts of organosilicon-modified nano-scale conductive titanium dioxide, 2-5 parts of foaming agent, 0.5-2 parts of foam stabilizer, and 0.3-0.5 parts of the above-mentioned polyurethane foaming catalyst; the component B is isocyanate.

[0053] In some embodiments, the polyether polyol has a hydroxyl value of 30-70 mgKOH / g, preferably 35-55 mgKOH / g.

[0054] In some embodiments, the hydroxyl value of the polyether polyol can be 35 mgKOH / g, 40 mgKOH / g, 45 mgKOH / g, 50 mgKOH / g, 55 mgKOH / g, or a range consisting of any two thereof.

[0055] In some embodiments, the organosilicon is selected from at least one of 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride and 3-(trimethoxysilyl)propyldimethylhexadecyl ammonium chloride.

[0056] Polyurethane sponge is prone to static electricity due to its electrical insulation. To solve this problem, the present invention uses organosilicon-modified nano-scale conductive titanium dioxide and a specific foam stabilizer to work together. The organosilicon-modified nano-scale conductive titanium dioxide is made by combining the hydrolyzed silanols of organosilicon (3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride and 3-(trimethoxysilyl)propyldimethylhexadecylammonium chloride) with the surface hydroxyls of the nano-scale conductive titanium dioxide. Organosilicon quaternary ammonium salt is grafted onto the nano-scale conductive titanium dioxide. The combined effect of the organosilicon-modified nano-scale conductive titanium dioxide and the organic silicon-modified nano-scale conductive titanium dioxide plays an anti-static role. At the same time, the organic silicon-modified nano-scale conductive titanium dioxide also avoids the agglomeration of the nano-scale conductive titanium dioxide in the polyurethane foam, thereby avoiding the decrease in the resilience of the polyurethane sponge and the increase in the cell collapse rate. The specific foam stabilizer (cyclic siloxane and polyether epoxy co-modified silicone oil) further avoids the decrease in the resilience of the polyurethane sponge and the increase in the cell collapse rate due to the addition of the organic silicon-modified nano-scale conductive titanium dioxide, and can also further improve the anti-static performance of the polyurethane foam.

[0057] In some embodiments, the particle size of the nano-scale conductive titanium dioxide is 50-250 nm.

[0058] In some embodiments, the preparation method of the organosilicon-modified nano-scale conductive titanium dioxide is as follows: nano-scale conductive titanium dioxide, organosilicon and water are mixed, stirred, washed and dried.

[0059] In some embodiments, the mass ratio of the nano-scale conductive titanium dioxide, silicone and water is (1.5-2):1:(15-20).

[0060] In some embodiments, the stirring conditions are: a rotation speed of 200-400 rpm, a temperature of 40-60° C., and a time of 6-10 h.

[0061] In some embodiments, the foaming agent is selected from at least one of water, cyclopentane, and n-pentane.

[0062] In some embodiments, the foam stabilizer comprises cyclic siloxane and polyether epoxy co-modified silicone oil in a mass ratio of (0.3-0.5):10.

[0063] In some embodiments, the cyclic siloxane is selected from at least one of 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0064] In some embodiments, the polyether epoxy co-modified silicone oil is selected from at least one of DY-ETE301 polyether epoxy co-modified silicone oil, DY-ETE302G-2 polyether epoxy co-modified silicone oil, DY-ETE302G2-T polyether epoxy co-modified silicone oil and DY-ETE301H polyether epoxy co-modified silicone oil produced by Shandong Dayi Chemical Co., Ltd.

[0065] In some embodiments, the isocyanate is selected from at least one of diphenylmethylene diisocyanate and toluene diisocyanate.

[0066] In some embodiments, the mass ratio of the polyether polyol to the isocyanate is 100:(30-60).

[0067] In some embodiments, the method for preparing the polyurethane sponge comprises the following steps: stirring and mixing the raw materials in component A evenly, adding component B, and stirring evenly to obtain a mixture; placing the mixture in a foaming mold and ripening to obtain the mixture.

[0068] In some embodiments, the aging temperature is 60° C., and the aging time is 2-4 minutes.

[0069] Example 1: This example provides a polyurethane foaming catalyst: 47g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 32g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), 6g of bis(dimethylaminopropylamine) isopropyl alcohol (Dingxin DXCAT@ZR50) and 5g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed uniformly to obtain a catalyst.

[0070] Example 2: This example provides a polyurethane foaming catalyst: 45g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 34g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), 5g of bis(dimethylaminopropylamine) isopropyl alcohol (Dingxin DXCAT@ZR50) and 6g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed uniformly to obtain a catalyst.

[0071] Comparative Example 1: Comparative Example 1-1 provides a catalyst for polyurethane foaming: 0g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 32g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), 6g of bis(dimethylaminopropylamine) isopropyl alcohol (Dingxin DXCAT@ZR50) and 5g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed evenly to obtain the catalyst.

[0072] Comparative Example 1-2 provides a polyurethane foaming catalyst: 47g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 0g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), 6g of bisdimethylaminopropylamine isopropyl alcohol (Dingxin DXCAT@ZR50) and 5g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed uniformly to obtain the catalyst.

[0073] Comparative Examples 1-3 provide a polyurethane foaming catalyst: 47 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310), 32 g of tetramethyldipropylenetriamine (POLYCAT@ 15), 6 g of bis(dimethylaminopropyl)amine isopropanol (Dingxin DXCAT@ZR50), and 5 g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070) are mixed uniformly to obtain the catalyst.

[0074] Comparative Examples 1-4 provide a polyurethane foaming catalyst: 40 g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 39 g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), 6 g of bisdimethylaminopropylamine isopropyl alcohol (Dingxin DXCAT@ZR50) and 5 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed uniformly to obtain the catalyst.

[0075] Comparative Example 2: Comparative Example 2-1 provides a catalyst for polyurethane foaming: 47g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 32g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), 0g of bis(dimethylaminopropylamine) isopropyl alcohol (Dingxin DXCAT@ZR50) and 5g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed evenly to obtain the catalyst.

[0076] Comparative Example 2-2 provides a polyurethane foaming catalyst: 47g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 32g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), 6g of bisdimethylaminopropylamine isopropyl alcohol (Dingxin DXCAT@ZR50) and 0g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed uniformly to obtain the catalyst.

[0077] Comparative Example 2-3 provides a polyurethane foaming catalyst: 47g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 32g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), and 11g of Evonik DABCO@NE-210 are mixed uniformly to obtain the catalyst.

[0078] Comparative Example 3: Comparative Example 3-1 provides a catalyst for polyurethane foaming: 45g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 28g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), 7g of bis(dimethylaminopropylamine) isopropyl alcohol (Dingxin DXCAT@ZR50) and 7g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed evenly to obtain the catalyst.

[0079] Comparative Example 3-2 provides a catalyst for polyurethane foaming: 48g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 30g of dimethylaminopropylamine diisopropyl alcohol (Dingxin DXCAT@DPA), 4g of bis(dimethylaminopropylamine) isopropyl alcohol (Dingxin DXCAT@ZR50) and 5g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed evenly to obtain the catalyst.

[0080] Application Example 1: A polyurethane sponge is composed of component A and component B: the component A, by mass, is composed of 100 parts of polyether polyol, 15 parts of organosilicon-modified nano-scale conductive titanium dioxide, 3 parts of foaming agent, 1.5 parts of foam stabilizer, and 0.4 parts of the catalyst of Example 1;

[0081] The hydroxyl value of the polyether polyol is 48±2 mgKOH / g (Zibo Dexin Federal Chemical Industry Co., Ltd.: DEP-455D).

[0082] The preparation method of the organosilicon-modified nano-scale conductive titanium dioxide is as follows: 1.8 g of nano-scale conductive titanium dioxide, 1 g of organosilicon (3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride, CAS No.: 27668-52-6) and 18 g of water are mixed, stirred at 300 rpm and 50° C. for 8 hours, washed, and dried to obtain the obtained product.

[0083] The particle size of the nano-scale conductive titanium dioxide is 50-100 nm (Shenzhen Zhongherun Technology Co., Ltd.).

[0084] The foaming agent is water.

[0085] The foam stabilizer is octamethylcyclotetrasiloxane (CAS No.: 556-67-2) and polyether epoxy co-modified silicone oil (Shandong Dayi Chemical Co., Ltd.: DY-ETE301 polyether epoxy co-modified silicone) in a mass ratio of 0.4:10.

[0086] The B component is toluene diisocyanate, and the mass ratio of the toluene diisocyanate to the polyether polyol is 100:32.

[0087] The preparation method of the polyurethane sponge comprises the following steps: stirring and mixing the raw materials in component A uniformly, adding component B, and stirring uniformly to obtain a mixture; placing the mixture in a foaming mold, and ripening at 60° C. for 3 minutes to obtain the mixture.

[0088] Application Example 2: A polyurethane sponge, which is different from Application Example 1 only in that the catalyst of Example 1 is replaced by the catalyst of Example 2 of the same mass; the rest are the same.

[0089] Comparative Application Example 1: Comparative Application Example 1-1: A polyurethane sponge, which differs from Application Example 1 only in that the catalyst in Example 1 is replaced by a catalyst of equal mass in Comparative Example 1-1; the rest are the same.

[0090] Comparative Application Example 1-2: A polyurethane sponge, which is different from Application Example 1 only in that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 1-2 of equal mass; the rest are the same.

[0091] Comparative Application Examples 1-3: A polyurethane sponge, which is different from Application Example 1 only in that the catalyst in Example 1 is replaced with the catalyst of Comparative Examples 1-3 of equal mass; the rest are the same.

[0092] Comparative Application Examples 1-4: A polyurethane sponge, which is different from Application Example 1 only in that the catalyst in Example 1 is replaced with the catalyst of Comparative Examples 1-4 of equal mass; the rest are the same.

[0093] Comparative Application Example 2: Comparative Application Example 2-1: A polyurethane sponge, which is different from Application Example 1 only in that the catalyst in Example 1 is replaced by the catalyst of Comparative Example 2-1 of equal mass; the rest are the same.

[0094] Comparative Application Example 2-2: A polyurethane sponge, which is different from Application Example 1 only in that the catalyst in Example 1 is replaced by the catalyst of Comparative Example 2-2 of equal mass; the rest are the same.

[0095] Comparative Application Example 2-3: A polyurethane sponge, which is different from Application Example 1 only in that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 2-3 of equal mass; the rest are the same.

[0096] Comparative Application Example 3: Comparative Application Example 3-1: A polyurethane sponge, which is different from Application Example 1 only in that the catalyst in Example 1 is replaced by a catalyst of equal mass in Comparative Example 3-1; the rest are the same.

[0097] Comparative Application Example 3-2: A polyurethane sponge, which is different from Application Example 1 only in that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 3-2 of equal mass; the rest are the same.

[0098] Comparative Application Example 4: A polyurethane sponge, which differs from Application Example 1 only in that the mass fraction of the catalyst is 0.8 parts; the rest are the same. Result: premature curing leads to deformation of the finished product and uneven structure of the finished product, such as Figure 2 shown.

[0099] Comparative Example Application Example 5: A polyurethane sponge, which is different from Application Example 1 only in that the polyether-epoxy co-modified silicone oil is replaced with a polyether-modified silicone oil of equal quality (Shandong Dayi Chemical Co., Ltd.: DY-ET123 polyether-modified silicone oil); the rest are the same.

[0100] Comparative Example 6: A polyurethane sponge, which differs from Application Example 1 only in that the organosilicon-modified nano-scale conductive titanium dioxide is replaced by nano-scale conductive titanium dioxide and 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride in a mass ratio of 1.8:1; the rest are the same.

[0101] Test Example 1: Laboratory Odor Level Evaluation: Six odor assessors were randomly selected to evaluate the odor level of the prepared polyurethane sponge according to the evaluation criteria in Table 1. The average of the results was shown in Table 2.

[0102] .

[0103] .

[0104] As can be seen from Table 2, the odor level of the polyurethane sponge of Application Example 1 and Application Example 2 can reach Level 2; while in Comparative Application Example 1, due to changes in the components or mass ratio of the main catalyst, Level 2 cannot be reached; in Comparative Application Example 2, due to changes in the components of the co-catalyst, Level 2 cannot be reached; in Comparative Application Example 3, due to the mass ratio of the main catalyst and the co-catalyst being outside the scope of protection of the present invention, Level 2 cannot be reached.

[0105] The test of Test Example 2 was continued on the polyurethane sponge with a laboratory odor level of 2-3.

[0106] Test Example 2: (1) The rebound rate of the polyurethane sponge was measured according to GB / T 6670-2008 Determination of rebound properties of flexible foam polymeric materials by falling ball method (Test Method A). The results are shown in Table 3.

[0107] (2) 100 polyurethane sponges were prepared using the same formula, and the cell collapse rate was calculated; cell collapse rate = polyurethane sponges with cell collapse / 100 × 100%. The results are shown in Table 3.

[0108] (3) Surface resistance: The surface resistance of the polyurethane sponge was tested according to ASTM D257 volume surface resistivity of insulating materials. The results are shown in Table 3.

[0109] .

[0110] As can be seen from Table 3, the polyurethane sponges of Application Example 1 and Application Example 2 have a rebound rate of more than 70%, a cell collapse rate of less than 5%, and a surface resistance of less than 10 6 Ω / sq; although the rebound rate of comparative application example 1-4 can reach 70%, its cell collapse rate is as high as 10%. Although the cell collapse rate of comparative application example 2-1 is only 6%, the rebound rate can only reach 65%. The rebound rate of comparative application example 3-2 can only reach 63% while the cell collapse rate is as high as 12%. Due to the change of foam stabilizer components in comparative application example 5 and the direct compounding of organic silicon and nano-conductive titanium dioxide in comparative application example 6, the rebound rate of the polyurethane sponge obtained cannot reach more than 70%, the cell collapse rate is more than 5%, and the surface resistance is higher than 10 6 Ω / sq or so.

[0111] Test Example 3: The polyurethane sponge of Application Example 1 was tested for its benzene, toluene, ethylbenzene, xylene, styrene, TVOC (C6-C16), formaldehyde, acetaldehyde, and acrolein contents, as well as its odor level after being placed at 65°C for 2 hours. The results are shown in Tables 4 and 5.

[0112] .

[0113] Note: 1. “*” indicates that toluene was used as the calibration substance for semi-quantitative analysis;

[0114] 2.ND means not detected (less than the detection limit);

[0115] 3. “Blank value” is the test result of a blank sampling bag.

[0116] .

[0117] Note: Judging criteria:

[0118] Level 1: No odor;

[0119] Level 2: There is an odor, but it is not disturbing;

[0120] Level 3: There is a noticeable odor, but it is still not disturbing;

[0121] Level 4: There is a disturbing odor;

[0122] Level 5: There is a strong disturbing odor;

[0123] Level 6: There is an unbearable odor.

[0124] Test Example 4: The polyurethane sponge of Application Example 2 was tested for its benzene, toluene, ethylbenzene, xylene, styrene, TVOC (C6-C16), formaldehyde, acetaldehyde, and acrolein contents, as well as its odor level after being placed at 65°C for 2 hours. The results are shown in Tables 6 and 7, respectively.

[0125] .

[0126] Note: 1. “*” indicates that toluene was used as a calibration substance for semi-quantitative analysis;

[0127] 2.ND means not detected (less than the detection limit);

[0128] 3. “Blank value” is the test result of a blank sampling bag.

[0129] .

[0130] Note: Judging criteria:

[0131] Level 1: No odor;

[0132] Level 2: There is an odor, but it is not disturbing;

[0133] Level 3: There is a noticeable odor, but it is still not disturbing;

[0134] Level 4: There is a disturbing odor;

[0135] Level 5: There is a strong disturbing odor;

[0136] Level 6: There is an unbearable odor.

[0137] It can be seen from Tables 4 to 7 that the polyurethane sponges of Application Examples 1 and 2 have lower contents of volatile harmful compounds, and the odor level can still reach Level 3 after being placed at 65° C. for 2 hours.

[0138] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A polyurethane foaming catalyst, characterized in that: The invention is composed of a main catalyst and a co-catalyst in a mass ratio of (6-8):1; the main catalyst is 3-dimethylaminopropyl urea and dimethylaminopropylamine diisopropyl alcohol; the co-catalyst is bisdimethylaminopropylamine isopropyl alcohol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether; The mass ratio of the 3-dimethylaminopropyl urea and dimethylaminopropylamine diisopropyl alcohol is (1.2-1.6):1; The mass ratio of the bis(dimethylaminopropyl)amine isopropyl alcohol to N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether is (1.1-1.3):

1.

2. The method for preparing the polyurethane foaming catalyst according to claim 1, wherein The following steps are involved: 3-Dimethylaminopropyl urea, dimethylaminopropylamine diisopropyl alcohol, bisdimethylaminopropylamine isopropyl alcohol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether are uniformly mixed to obtain the product.

3. A polyurethane sponge comprising component A and component B; characterized in that: The component A comprises, by mass, 100 parts of polyether polyol, 10-20 parts of organosilicon-modified nano-conductive titanium dioxide, 2-5 parts of foaming agent, 0.5-2 parts of foam stabilizer, and 0.3-0.5 parts of the polyurethane foaming catalyst according to claim 1; the component B is isocyanate.

4. The polyurethane sponge according to claim 3, characterized in that The hydroxyl value of the polyether polyol is 30-70 mgKOH / g.

5. The polyurethane sponge according to claim 4, characterized in that The organosilicon is selected from at least one of 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride and 3-(trimethoxysilyl)propyldimethylhexadecylammonium chloride.

6. The polyurethane sponge according to claim 5, characterized in that The preparation method of the organosilicon-modified nano-scale conductive titanium dioxide is as follows: the nano-scale conductive titanium dioxide, organosilicon and water are mixed, stirred, washed and dried.

7. The polyurethane sponge according to claim 6, characterized in that The foam stabilizer comprises cyclic siloxane and polyether epoxy co-modified silicone oil in a mass ratio of (0.3-0.5):

10.

8. The polyurethane sponge according to claim 7, characterized in that The cyclic siloxane is selected from at least one of 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

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