Catalyst for polyurethane foaming, preparation method and polyurethane sponge

Abstract

The invention belongs to the technical field of polyurethane foaming, and particularly relates to a catalyst for polyurethane foaming, a preparation method and polyurethane sponge. The catalyst for polyurethane foaming consists of a main catalyst and a cocatalyst in a mass ratio of (6-8): 1, the main catalyst is 3-(dimethylamino) propyl urea and dimethylamino propylamine diisopropyl alcohol; the cocatalyst is bis (dimethylamino) propyl amine isopropanol and N, N, N '-trimethyl-N'-(2-ethoxyl) bis (2-aminoethyl) ether, and polyurethane foam prepared by using the catalyst has the advantages of low odor, low content of volatile harmful compounds, high rebound rate, low cell collapse rate and good antistatic performance.

Description

Technical Field

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

[0002] Polyurethane foaming materials have the advantages of light weight, heat insulation, good resilience, breathability, etc., and have broad application prospects in the automotive field. For example, polyurethane flexible foams can be used as automotive seat cushions, backrests, headrests, decorative strips, and polyurethane rigid foams can be used as door panel linings, sun visors, ceiling linings, etc.

[0003] In recent years, with the continuous improvement of people's requirements for automotive quality and environmental protection, the requirements for polyurethane foaming materials have also become higher and higher, especially the attention to the odor and VOC content of polyurethane foaming materials has increased.

[0004] The raw materials of polyurethane foaming materials usually include polyether polyols, polymer polyols, isocyanates, catalysts, etc. The sources of their odor and VOC are mainly the volatile monomers remaining in the polyether polyols and polymer polyols. In addition, the commonly used tertiary amine catalysts in polyurethane foaming materials, although their dosage in polyurethane foaming materials is very small, because they do not participate in the reaction, after the reaction is completed, they will remain in the porous structure of the polyurethane foaming materials, and their volatility will cause the odor of the polyurethane foaming materials to be large and the VOC content to be high.

[0005] In the prior art, in order to reduce the odor and VOC content of polyurethane foaming materials, low-volatility tertiary amine catalysts are often used. For example, Chinese Patent No. CN109485820A discloses a low-odor and low-VOC polyurethane high-resilience foam. Suitable low-volatility tertiary amine catalysts include NE series non-dispersive catalysts such as NE300 and NE1070 of Evonik Corporation (formerly Air Products and Chemicals, Inc.), EF series products such as EF602, EF608, EF150, and EF680 of Momentive Performance Materials Inc., products such as ZR-50 and DPA of Huntsman Corporation, and one or more of similar products sold by other companies on the market. Chinese Patent No. CN116789925A discloses a formaldehyde-free and low-odor polyurethane foam material and a preparation method thereof. The low-odor catalyst is a mixture of a reactive catalyst, an odorless and low-volatile balance catalyst, and a delayed amine catalyst; the reactive catalyst includes at least one of N,N,N-trimethyl-N-hydroxyethyl bis(aminoethyl ether) (JEFFCAT ZF-10) and tetramethyldipropylenetriamine (TMBPA), the odorless and low-volatile balance 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, all of the above technical solutions require the use of specific polyols and aldehyde cleaning agents in combination with low-odor catalysts to achieve an odor level of 3.5. Summary of the Invention

[0007] The present invention aims to solve one or more technical problems existing in the above-mentioned prior art and provides at least one beneficial option. Specifically, the present invention provides a catalyst for polyurethane foaming, a preparation method thereof, and a polyurethane sponge. The polyurethane foam prepared with this catalyst has low odor, low content of volatile harmful compounds, high resilience, low cell collapse rate, and good antistatic performance.

[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 with a mass ratio of (6-8):1; the main catalyst is 3-dimethylaminopropylurea and dimethylaminopropylamine diisopropanol; the co-catalyst is bis(dimethylaminopropyl)amine isopropanol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether.

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

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

[0011] The CAS number of bis(dimethylaminopropyl)amine isopropanol 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 3-dimethylaminopropylurea to dimethylaminopropylamine diisopropanol is (1.2-1.6):1.

[0014] Optionally, the mass ratio of bis(dimethylaminopropyl)amine isopropanol 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 preparation method of the above catalyst for polyurethane foaming, which includes the following steps: mixing 3-dimethylaminopropylurea, dimethylaminopropylamine diisopropanol, bis(dimethylaminopropyl)amine isopropanol, and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether evenly to obtain the catalyst.

[0016] On the other hand, the present invention provides a polyurethane sponge, comprising component A and component B; Component A, by mass, comprises 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 above-mentioned catalyst for polyurethane foaming; Component B is isocyanate.

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

[0018] Optionally, the organosilicon is selected from at least one of 3-(trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride and 3-(trimethoxysilyl) propyl dimethyl hexadecyl ammonium chloride.

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

[0020] Optionally, the preparation method of the organosilicon-modified nano-conductive titanium dioxide is: mixing nano-conductive titanium dioxide, organosilicon and water, stirring, washing, and drying to obtain.

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

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

[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 with 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 diphenylmethane 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 includes 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 curing to obtain the product.

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

[0031] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention uses 3-dimethylaminopropylurea and dimethylaminopropylamine diisopropanol as the main catalyst and the co-catalyst (bis-dimethylaminopropylamine isopropanol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether) in combination. The odor grade of the prepared polyurethane foam can reach level 2, and the odor grade can reach level 3 after being placed at 65°C for 2 h. Moreover, under the condition of not using specific polyether polyols and aldehyde cleaning agents, it has a low content of volatile harmful compounds.

[0032] 2. The present invention uses organosilicon-modified nano-scale conductive titanium dioxide and a specific foam stabilizer (cyclic siloxane and polyether epoxy co-modified silicone oil) to act together, enabling the polyurethane sponge to have excellent antistatic performance (the surface resistance is about 10 6 Ω / sq) while avoiding the decline of the rebound performance of the polyurethane sponge (the rebound rate can reach more than 70%) and avoiding the increase of the cell collapse rate (the cell collapse rate is below 5%). Description of the Drawings

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required to be used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present application and should not be regarded as limiting the scope of the present application.

[0034] Figure 1 It is a physical diagram of the polyurethane sponge prepared in Application Example 1 of the present invention.

[0035] Figure 2 It is a physical diagram of the polyurethane sponge prepared in Comparative Application Example 4 of the present invention.

[0036] Figure 3 It is a physical diagram of the polyurethane sponge with cell collapse prepared in Comparative Application Example 6 of the present invention. Detailed Embodiments

[0037] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. For those not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are adopted. For the reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0038] 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 with a mass ratio of (6-8):1; the main catalyst is 3-dimethylaminopropylurea and dimethylaminopropylamine diisopropanol; the co-catalyst is bis-dimethylaminopropylamine isopropanol and N,N,N'-trimethyl-N'-(2-hydroxyethyl) bis(2-aminoethyl) ether.

[0039] There are dozens or hundreds of known catalysts for polyurethane foaming in the art, but not any catalyst can obtain polyurethane foam with low odor; in order to reduce the curing temperature and odor after polyurethane foaming, the inventor unexpectedly found during the experiment that using 3-dimethylaminopropylurea and dimethylaminopropylamine diisopropanol as the main catalyst and co-catalyst (bis-dimethylaminopropylamine isopropanol and N,N,N'-trimethyl-N'-(2-hydroxyethyl) bis(2-aminoethyl) ether) in combination can, while balancing the foaming and gel reactions, combine with isocyanate to reduce the volatilization of the catalyst. 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. Moreover, under the condition of not using specific polyether polyols and aldehyde cleaners, it has a low content of volatile harmful compounds.

[0040] In some embodiments, the mass ratio of the main catalyst to the co-catalyst can be 6:1, 7:1, 8:1, or the range composed of any two of them.

[0041] In some embodiments, the mass ratio of 3-dimethylaminopropylurea to dimethylaminopropylamine diisopropanol is (1.2-1.6):1.

[0042] In some embodiments, the mass ratio of bis-dimethylaminopropylamine isopropanol to N,N,N'-trimethyl-N'-(2-hydroxyethyl) bis(2-aminoethyl) ether is (1.1-1.3):1.

[0043] The preferred catalyst of the present invention needs to strictly control the mass ratio of the main catalyst to the co-catalyst and the mass ratio of 3-dimethylaminopropylurea to dimethylaminopropylamine diisopropanol, otherwise it will cause the odor of the polyurethane foam to increase and at the same time affect the rebound rate and cell collapse rate of the polyurethane foam.

[0044] In some embodiments, the mass ratio of the 3-dimethylaminopropyl urea to the dimethylaminopropylamine diisopropanol can be 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, or a range composed of any two of them.

[0045] In some embodiments, the 3-dimethylaminopropyl urea is selected from at least one of Dingxin DXCAT@NE1070 and Evonik DABCO@NE1070.

[0046] In some embodiments, the dimethylaminopropylamine diisopropanol is selected from at least one of Dingxin DXCAT@DPA, Huntsman JEFFCAT@DPA, and Evonik DABCO@NE1050.

[0047] In some embodiments, the mass ratio of the bis(dimethylaminopropyl)amine isopropanol to the 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 composed of any two of them.

[0048] In some embodiments, the bis(dimethylaminopropyl)amine isopropanol is selected from at least one of Dingxin DXCAT@ZR50 and Huntsman JEFFCAT@ZR50.

[0049] In some embodiments, the N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether is Evonik DABCO@NE-310.

[0050] On the other hand, the present invention provides a preparation method of the above-mentioned catalyst for polyurethane foaming, including the following steps: uniformly mixing 3-dimethylaminopropyl urea, dimethylaminopropylamine diisopropanol, bis(dimethylaminopropyl)amine isopropanol, and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether to obtain the product.

[0051] On yet another aspect, the present invention provides a polyurethane sponge, including component A and component B; component A, by mass, includes 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 catalyst for polyurethane foaming; component B is isocyanate.

[0052] In some embodiments, the hydroxyl value of the polyether polyol is 30 - 70 mgKOH / g, preferably 35 - 55 mgKOH / g.

[0053] 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 the range composed of any two of them.

[0054] In some embodiments, the silicone is selected from at least one of 3-(trimethoxysilyl)propyl dimethyloctadecyl ammonium chloride and 3-(trimethoxysilyl)propyl dimethylhexadecyl ammonium chloride.

[0055] Due to its electrical insulation, polyurethane sponge is prone to generating static electricity. To solve this problem, the present invention uses the combined action of organosilicon-modified nano-conductive titanium dioxide and a specific foam stabilizer. Among them, the organosilicon-modified nano-conductive titanium dioxide is formed by combining the silanol groups hydrolyzed from organosilicon (3-(trimethoxysilyl)propyl dimethyloctadecyl ammonium chloride and 3-(trimethoxysilyl)propyl dimethylhexadecyl ammonium chloride) with the hydroxyl groups on the surface of nano-conductive titanium dioxide, grafting organosilicon quaternary ammonium salt onto the nano-conductive titanium dioxide. The combined action of the organosilicon quaternary ammonium salt and the nano-conductive titanium dioxide plays an antistatic role. At the same time, the organosilicon-modified nano-conductive titanium dioxide also avoids the agglomeration of nano-conductive titanium dioxide in the polyurethane foam, thus avoiding the decline in the rebound performance 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 decline in the rebound performance of the polyurethane sponge and the increase in the cell collapse rate caused by the addition of the organosilicon-modified nano-conductive titanium dioxide, and can further improve the antistatic performance of the polyurethane foam.

[0056] In some embodiments, the particle size of the nano-conductive titanium dioxide is 50 - 250 nm.

[0057] In some embodiments, the preparation method of the organosilicon-modified nano-conductive titanium dioxide is: mixing nano-conductive titanium dioxide, organosilicon and water, stirring, washing, and drying to obtain it.

[0058] In some embodiments, the mass ratio of the nano-conductive titanium dioxide, organosilicon and water is (1.5 - 2):1:(15 - 20).

[0059] In some embodiments, the conditions for stirring are: the rotation speed is 200 - 400 rpm, the temperature is 40 - 60 °C, and the time is 6 - 10 h.

[0060] In some embodiments, the blowing agent is selected from at least one of water, cyclopentane, and n-pentane.

[0061] In some embodiments, the foam stabilizer includes cyclic siloxane and polyether epoxy co-modified silicone oil with a mass ratio of (0.3 - 0.5):10.

[0062] In some embodiments, the cyclic siloxane is selected from at least one of 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0063] 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.

[0064] In some embodiments, the isocyanate is selected from at least one of diphenylmethane diisocyanate and toluene diisocyanate.

[0065] In some embodiments, the mass ratio of the polyether polyol to the isocyanate is 100:(30 - 60).

[0066] 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 curing to obtain the product.

[0067] In some embodiments, the temperature of curing is 60°C and the time of curing is 2 - 4 min.

[0068] Example 1: This example provides a catalyst for polyurethane foaming: 47 g of 3-dimethylaminopropylurea (Dingxin DXCAT@NE1070), 32 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 6 g of bis-dimethylaminopropylamine isopropanol (Dingxin DXCAT@ZR50), and 5 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed evenly to obtain the product.

[0069] Example 2: This example provides a catalyst for polyurethane foaming: 45 g of 3-dimethylaminopropylurea (Dingxin DXCAT@NE1070), 34 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 5 g of bis-dimethylaminopropylamine isopropanol (Dingxin DXCAT@ZR50), and 6 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed evenly to obtain the product.

[0070] Comparative Example 1: Comparative Example 1-1 provided a catalyst for polyurethane foaming: 0 g of 3-dimethylaminopropylurea (Dingxin DXCAT@NE1070), 32 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 6 g of bis(dimethylaminopropyl)amine isopropanol (Dingxin DXCAT@ZR50), and 5 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) were mixed evenly to obtain the catalyst.

[0071] Comparative Example 1-2 provided a catalyst for polyurethane foaming: 47 g of 3-dimethylaminopropylurea (Dingxin DXCAT@NE1070), 0 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 6 g of bis(dimethylaminopropyl)amine isopropanol (Dingxin DXCAT@ZR50), and 5 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) were mixed evenly to obtain the catalyst.

[0072] Comparative Example 1-3 provided a catalyst for polyurethane foaming: 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-dimethylaminopropylurea (Dingxin DXCAT@NE1070) were mixed evenly to obtain the catalyst.

[0073] Comparative Example 1-4 provided a catalyst for polyurethane foaming: 40 g of 3-dimethylaminopropylurea (Dingxin DXCAT@NE1070), 39 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 6 g of bis(dimethylaminopropyl)amine isopropanol (Dingxin DXCAT@ZR50), and 5 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) were mixed evenly to obtain the catalyst.

[0074] Comparative Example 2: Comparative Example 2-1 provided a catalyst for polyurethane foaming: 47 g of 3-dimethylaminopropylurea (Dingxin DXCAT@NE1070), 32 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 0 g of bis(dimethylaminopropyl)amine isopropanol (Dingxin DXCAT@ZR50), and 5 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) were mixed evenly to obtain the catalyst.

[0075] Comparative Example 2-2 provides a catalyst for polyurethane foaming: 47 g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 32 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 6 g of bis(dimethylaminopropyl)amine isopropanol (Dingxin DXCAT@ZR50), and 0 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed evenly to obtain it.

[0076] Comparative Example 2-3 provides a catalyst for polyurethane foaming: 47 g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 32 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 11 g of Evonik DABCO@NE-210 are mixed evenly to obtain it.

[0077] Comparative Example 3: Comparative Example 3-1 provides a catalyst for polyurethane foaming: 45 g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 28 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 7 g of bis(dimethylaminopropyl)amine isopropanol (Dingxin DXCAT@ZR50), and 7 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed evenly to obtain it.

[0078] Comparative Example 3-2 provides a catalyst for polyurethane foaming: 48 g of 3-dimethylaminopropyl urea (Dingxin DXCAT@NE1070), 30 g of dimethylaminopropylamine diisopropanol (Dingxin DXCAT@DPA), 4 g of bis(dimethylaminopropyl)amine isopropanol (Dingxin DXCAT@ZR50), and 5 g of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl) ether (Evonik DABCO@NE-310) are mixed evenly to obtain it.

[0079] Application Example 1: A polyurethane sponge is composed of Component A and Component B. Component A, by mass, consists 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 part of the catalyst of Example 1. The hydroxyl value of the polyether polyol is 48 ± 2 mgKOH / g (Zibo Dexin Federal Chemical Industry Co., Ltd.: DEP-455D).

[0080] The preparation method of the silicone-modified nano-conductive titanium dioxide is as follows: 1.8 g of nano-conductive titanium dioxide, 1 g of silicone (3-(trimethoxysilyl)propyl dimethyloctadecylammonium chloride, CAS No.: 27668-52-6), and 18 g of water are mixed, stirred at 300 rpm and 50 °C for 8 h, washed, and dried to obtain the product.

[0081] The particle size of the nano-conductive titanium dioxide is 50 - 100 nm (Shenzhen Zhongherun Technology Co., Ltd.).

[0082] The blowing agent is water.

[0083] 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) with a mass ratio of 0.4:10.

[0084] The component B is toluene diisocyanate, and the mass ratio of the toluene diisocyanate to the polyether polyol is 100:32.

[0085] The preparation method of the polyurethane sponge includes the following steps: The raw materials in component A are stirred and mixed evenly, component B is added, and stirred evenly to obtain a mixture; the mixture is placed in a foaming mold and cured at 60 °C for 3 min to obtain the product.

[0086] Application Example 2: A polyurethane sponge, the difference from Application Example 1 is only that the catalyst in Example 1 is replaced with the catalyst of Example 2 with the same mass; the rest are the same.

[0087] Comparative Application Example 1: Comparative Application Example 1-1: A polyurethane sponge, the difference from Application Example 1 is only that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 1-1 with the same mass; the rest are the same.

[0088] Comparative Application Example 1-2: A polyurethane sponge, the difference from Application Example 1 is only that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 1-2 with the same mass; the rest are the same.

[0089] Comparative Application Example 1-3: A polyurethane sponge, the difference from Application Example 1 is only that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 1-3 with the same mass; the rest are the same.

[0090] Comparative Application Example 1-4: A polyurethane sponge, the difference from Application Example 1 is only that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 1-4 with the same mass; the rest are the same.

[0091] Comparative Application Example 2: Comparative Application Example 2-1: A polyurethane sponge, the difference from Application Example 1 is only that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 2-1 with the same mass; the rest are the same.

[0092] Comparative Application Example 2-2: A polyurethane sponge, the difference from Application Example 1 is only that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 2-2 with the same mass; the rest are the same.

[0093] Comparative Application Example 2-3: A polyurethane sponge, the difference from Application Example 1 is only that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 2-3 with the same mass; the rest are the same.

[0094] Comparative Application Example 3: Comparative Application Example 3-1: A polyurethane sponge, the difference from Application Example 1 is only that the catalyst in Example 1 is replaced with the catalyst of Comparative Example 3-1 with the same mass; the rest are the same.

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

[0096] Comparative Application Example 4: A polyurethane sponge, the difference from Application Example 1 is only that the mass fraction of the catalyst is 0.8 parts; the rest are the same. Result: Premature curing led to deformation of the finished product, and the structure of the finished product was uneven, as Figure 2 shown.

[0097] Comparative Application Example 5: A polyurethane sponge, the difference from Application Example 1 is only that the polyether epoxy co-modified silicone oil is replaced with the polyether-modified silicone oil of the same mass (Shandong Dayi Chemical Co., Ltd.: DY-ET123 polyether-modified silicone oil); the rest are the same.

[0098] Comparative Application Example 6: A polyurethane sponge, the difference from Application Example 1 is only that the organosilicon-modified nano-conductive titanium dioxide is replaced with nano-conductive titanium dioxide with a mass ratio of 1.8:1 and 3-(trimethoxysilyl) propyldimethyloctadecylammonium chloride; the rest are the same.

[0099] Test Example 1: Laboratory odor level evaluation: Randomly select 6 odor discriminators, and judge the odor level of the prepared polyurethane sponge according to the judgment criteria in Table 1, and take the average. The results are shown in Table 2.

[0100] 。

[0101] 。

[0102] As can be seen from Table 2, the odor grades of the polyurethane sponges in Application Example 1 and Application Example 2 can reach Grade 2; while in Comparative Application Example 1, due to the change in the components or mass ratio of the main catalyst, it cannot reach Grade 2; in Comparative Application Example 2, due to the change in the components of the co-catalyst, it cannot reach Grade 2; in Comparative Application Example 3, due to the mass ratio of the main catalyst and the co-catalyst not being within the scope protected by the present invention, it cannot reach Grade 2.

[0103] The polyurethane sponges with a laboratory odor grade of 2-3 were continuously tested according to Test Example 2.

[0104] Test Example 2: (1) The rebound rate of the polyurethane sponge was measured according to GB / T 6670-2008 Determination of Rebound Performance of Flexible Cellular Materials by the Falling Ball Method (Test Method A), and the results are shown in Table 3; (2) 100 polyurethane sponges were prepared using the same formula, and the cell collapse rate was calculated; the cell collapse rate = the number of polyurethane sponges with cell collapse / 100 × 100%, and the results are shown in Table 3; (3) Surface resistance: The surface resistance of the polyurethane sponge was measured according to ASTM D257 Volume and Surface Resistivity of Insulating Materials, and the results are shown in Table 3.

[0105] 。

[0106] As can be seen from Table 3, the rebound rate of the polyurethane sponges in Application Example 1 and Application Example 2 can reach more than 70%, the cell collapse rate is below 5%, and the surface resistance is around 10 6 Ω / sq; although the rebound rate of Comparative Application Examples 1-4 can reach 70%, their 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 in the components of the foam stabilizer in Comparative Application Example 5 and due to the direct compounding of silicone and nanoscale conductive titanium dioxide in Comparative Application Example 6, the rebound rate of the obtained polyurethane sponges cannot reach more than 70%, the cell collapse rate is above 5%, and the surface resistance is higher than 10 6 Ω / sq.

[0107] Test Example 3: Detect the contents of benzene, toluene, ethylbenzene, xylene, styrene, TVOC (C6-C16), formaldehyde, acetaldehyde, and acrolein in the polyurethane sponge of Application Example 1 and its odor grade after being placed at 65°C for 2 h, and the results are shown in Tables 4 and 5.

[0108] 。

[0109] Remark: 1. "*" indicates semi-quantitative analysis using toluene as a calibration substance; 2. N.D. indicates not detected (less than the detection limit); 3. The "blank value" is the test result of the blank sampling bag.

[0110] 。

[0111] Remark: Evaluation criteria: Grade 1: Odorless; Grade 2: Has an odor, but no interference; Grade 3: Has an obvious odor, but still no interference; Grade 4: Has an interfering odor; Grade 5: Has a strong interfering odor; Grade 6: Has an unbearable odor.

[0112] Test Example 4: Detect the contents of benzene, toluene, ethylbenzene, xylene, styrene, TVOC (C6 - C16), formaldehyde, acetaldehyde, and acrolein in the polyurethane sponge of Application Example 2, as well as the odor grade after being placed at 65 °C for 2 h. The results are shown in Table 6 and Table 7 respectively.

[0113] 。

[0114] Remark: 1. "*" indicates semi - quantitative analysis using toluene as the calibration substance; 2. N.D. indicates not detected (less than the detection limit); 3. The "blank value" is the test result of the blank sampling bag.

[0115] 。

[0116] Remark: Evaluation criteria: Grade 1: Odorless; Grade 2: Has an odor, but no interference; Grade 3: Has an obvious odor, but still no interference; Grade 4: Has an interfering odor; Grade 5: Has a strong interfering odor; Grade 6: Has an unbearable odor.

[0117] It can be seen from Table 4 - Table 7 that the polyurethane sponges of Application Example 1 and Application Example 2 have relatively low contents of volatile harmful compounds, and the odor grade can still reach Grade 3 after being placed at 65 °C for 2 h.

[0118] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than limiting the protection scope of the present invention. Any simple modification or equivalent replacement made by those of ordinary skill in the art to the technical solution of the present invention shall not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A catalyst for polyurethane foaming, characterized in that, It is composed of a main catalyst and a co-catalyst with a mass ratio of (6 - 8):1; the main catalyst is 3-dimethylaminopropylurea and dimethylaminopropylamine diisopropanol; the co-catalyst is bis(dimethylaminopropyl)amine isopropanol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether.

2. The catalyst for polyurethane foaming according to claim 1, characterized in that, The mass ratio of the 3-dimethylaminopropylurea to the dimethylaminopropylamine diisopropanol is (1.2 - 1.6):

1.

3. The catalyst for polyurethane foaming according to claim 2, characterized in that, The mass ratio of the bis(dimethylaminopropyl)amine isopropanol to the N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether is (1.1 - 1.3):

1.

4. The preparation method of the catalyst for polyurethane foaming according to any one of claims 1-3, characterized in that, It includes the following steps: Mix 3-dimethylaminopropylurea, dimethylaminopropylamine diisopropanol, bis(dimethylaminopropyl)amine isopropanol and N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether evenly to obtain it.

5. A polyurethane sponge, comprising component A and component B; characterized in that, The component A, by mass parts, includes 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 polyurethane foaming catalyst according to any one of claims 1 - 3; the component B is isocyanate.

6. The polyurethane sponge according to claim 5, wherein The hydroxyl value of the polyether polyol is 30 - 70mgKOH / g.

7. The polyurethane sponge according to claim 6, characterized in that, The organosilicon is selected from at least one of 3-(trimethoxysilyl)propyl dimethyloctadecylammonium chloride and 3-(trimethoxysilyl)propyl dimethylhexadecylammonium chloride.

8. The polyurethane sponge according to claim 7, characterized in that, The preparation method of the organosilicon-modified nano-scale conductive titanium dioxide is: mix nano-scale conductive titanium dioxide, organosilicon and water, stir, wash, and dry to obtain it.

9. The polyurethane sponge according to claim 8, wherein The foam stabilizer includes cyclic siloxane and polyether epoxy co-modified silicone oil with a mass ratio of (0.3 - 0.5):

10.

10. The polyurethane sponge according to claim 9, 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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