A polyurethane elastomeric mat and a continuous method of making the same

Abstract

The application belongs to the technical field of polyurethane, and proposes a polyurethane elastic pad plate and a continuous preparation method thereof.Raw materials are selected by selecting a polyether polyol and an isocyanate component formula, and after mixing, the raw materials are directly poured on the surface of a steel belt machine, self-leveling, free foaming, and then curing and forming, and finally cutting into different sizes, so that the production efficiency is high, no mold opening is needed, and the product size can be cut according to the needs.Through the above technical scheme, the problem of rough and uneven cell of the elastic pad plate in the prior art is solved.

Description

Technical Field

[0001] This invention belongs to the field of polyurethane technology and relates to a polyurethane elastic pad and its continuous preparation method. Background Technology

[0002] Currently, polyurethane elastic pads are microporous foamed elastomer materials. Their preparation methods mostly adopt molding processes, in which isocyanate and polyether polyol are mixed in a foaming machine and poured into a preheated mold cavity. After molding, the mixture is cured and shaped, and after demolding, the edges are trimmed to obtain the finished product.

[0003] The commonly used technique involves directly mixing the materials and using a low-pressure foaming machine to pour the materials into a fixed mold cavity. After the mold is closed, the material foams and matures, and then the edges are trimmed after demolding. This results in low production efficiency, requiring multiple molds to be used repeatedly; it can only produce products of fixed sizes, and new molds are needed to change the size; it cannot produce pads with large widths, thicknesses, and arbitrary lengths suitable for continuous laying; and the uniformity of the foam cells after low-pressure mixing and foaming is poor.

[0004] Furthermore, current applications place higher demands on the strength of polyurethane elastic pads, making it particularly important to develop and produce polyurethane materials with higher mechanical properties. Summary of the Invention

[0005] This invention proposes a polyurethane elastic pad and its continuous preparation method, which solves the problems of rough foam cells and uneven foam cell structure in the prior art. At the same time, the polyurethane elastic pad has higher strength.

[0006] The technical solution of this invention is implemented as follows:

[0007] A polyurethane elastic pad, the raw materials of which include a polyol component and an isocyanate component in a mass ratio of 100:70-100;

[0008] The polyol component includes: 50-70 parts polymer polyol, 10-15 parts chain extender, 1-5 parts hollow glass microspheres, 0.1-0.5 parts foam stabilizer, 0.5-3 parts antioxidant, 0.5-2 parts cell inducing agent, 0.1-1 part flow promoter, and 0.5-3 parts catalyst.

[0009] The cell inducing agent is prepared by reacting 30-50 parts of 3-isocyanate propyltrimethoxysilane, 10-40 parts of nano-Al2O3 and 20-30 parts of polybutadiene-acrylonitrile copolymer.

[0010] The flow promoter is prepared by reacting 30-50 parts of hydroxyl-terminated and / or amino-terminated polydimethylsiloxane, 15-30 parts of hexamethylene diisocyanate, 5-15 parts of 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate, 5-10 parts of diethylene glycol and 10-30 parts of toluene.

[0011] The polymer polyol is selected from polyols with a number average molecular weight of 1000-6000 and a functionality of 2 or 3.

[0012] Further, the preparation method of the cell inducing agent includes the following steps: adding 30-50 parts of 3-isocyanate propyltrimethoxysilane to 50-80 parts of ethyl acetate, then uniformly adding 10-40 parts of nano-Al2O3 over 10-20 minutes, uniformly heating to 45-65℃ over 15 minutes, stirring at 200 r / min, and reacting for 2-3 hours; then adding 20-30 parts of polybutadiene-acrylonitrile copolymer, reacting for 2-6 hours, heating to 80-100℃, with a vacuum degree not lower than 0.6 MPa, and distilling the ethyl acetate under reduced pressure to obtain the cell inducing agent.

[0013] Furthermore, the stirring speed is 150-250 r / min.

[0014] Furthermore, the stirring speed is 200 r / min.

[0015] Further, the preparation method of the flow promoter includes the following steps: dehydrating bis(3-aminopropyl)-terminated polydimethylsiloxane and / or bis(hydroxyalkyl)-terminated polydimethylsiloxane at 80-100℃ and a vacuum degree of not less than 0.8MPa for 1-3h, cooling to below 60℃, adding hexamethylene diisocyanate, stirring and reacting at 70-95℃ for 3-4h, adding toluene and stirring for 30min, then adding diethylene glycol and stirring and reacting for 2-3h, and finally adding 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate and stirring and reacting for 2-4h to obtain the flow promoter.

[0016] The structural formula of the bi(hydroxyalkyl)-terminated polydimethylsiloxane is as follows:

[0017] ,

[0018] The preferred product is IOTA 2030-10 silicone oil, purchased from Anhui Aiyota Silicone Oil Co., Ltd., with a molecular weight of 1000.

[0019] The structural formula of the bis(3-aminopropyl)-terminated polydimethylsiloxane is as follows:

[0020] ;

[0021] The preferred product is SILONG 8100, with a molecular weight of 1000, purchased from Hangzhou Sloan Materials Technology Co., Ltd.

[0022] Furthermore, the stirring speed is 150-250 r / min.

[0023] Furthermore, the stirring speed is 200 r / min.

[0024] Furthermore, the polymeric polyol is a mixture of polyether polyol and polytetrahydrofuran diol with a mass ratio of 7:3 and a number average molecular weight of 1000 (functionality 2).

[0025] The polyether polyol is a mixture of polyether polyols with a trifunctionality of 3000 number-average molecular weight, trifunctionality of 5000 number-average molecular weight, and trifunctionality of 6000 number-average molecular weight in a mass ratio of 5:3:2.

[0026] The chain extender is a mixture of a diol chain extender and a polyether polyol with a functionality of 400 in a mass ratio of 6:4.

[0027] The diol chain extender is selected from one or a mixture of several of the following: neopentyl glycol monoester of hydroxypentanoic acid, 3-methyl-1,5-pentanediol, and 1,4-dihydroxymethylcyclohexane.

[0028] The hollow glass microspheres have a particle size of 20-500 μm and a bulk density of 0.3-0.4 g / cm³. 3 ;

[0029] The foam stabilizer is selected from one or a mixture of several of the following: M-8843, M-8804, M-8842, M-7771LF2, M-7738LF2, M-7731 and M-7730 from Jiangsu Meiside Chemical Co., Ltd.

[0030] The antioxidant is a mixture of antioxidant 1010 and ultraviolet absorber UV328 in a mass ratio of 2:1;

[0031] The particle size of the nano-Al2O3 is 100-1000 nm;

[0032] The catalyst composition includes 10-40 wt% amine tin catalyst and 60-90 wt% liquid paraffin; the amine tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2; the organotin is stannous octoate and / or dibutyltin dilaurate.

[0033] Furthermore, the foaming agent is component A and component B in a mass ratio of 8:2. Component A is selected from one of M-8843, M-8804, and M-8842 from Jiangsu Meiside Chemical Co., Ltd., and component B is selected from one of M-7771LF2, M-7738LF2, M-7731, and M-7730.

[0034] Further, the isocyanate component includes:

[0035] 30-40 parts toluene diisocyanate (WANNATE TDI-80, Wanhua Chemical).

[0036] 20-25 parts diphenylmethane diisocyanate (WANNATE MDI-100 from Wanhua Chemical).

[0037] 20-30 parts of diphenylmethane diisocyanate (WANNATE MDI-50) and / or carbodiimide-modified diphenylmethane diisocyanate (WANNATECDMDI-100H).

[0038] 10-20 parts of polytetrahydrofuran ether diol (BASF PolyTHF 1000).

[0039] Further, the preparation method of the polyol component includes: preparing raw materials according to the formula, mixing and dispersing the polymer polyol, chain extender and antioxidant at a stirring speed of 200 r / min for 30 min, then grinding to a fineness of less than 15 μm, then heating to 105-110℃ and continuing to stir for 30 min; cooling to below 70℃, then adding hollow glass microspheres, foam stabilizer, foam inducing agent, flow promoter and catalyst, continuing to mix and stir for 0.5-1 h, and then adjusting the water content to 0.15-0.25 wt% to obtain the polyol component.

[0040] Furthermore, the stirring speed is 150-250 r / min.

[0041] Furthermore, the stirring speed is 200 r / min.

[0042] Furthermore, the polyol component is mixed and dissolved with 5-40% by volume of dry inert gas before use; wherein the mixing parameters are as follows: the temperature of the polyol is controlled at 35-55℃, the flow rate is 4-20L / min, the flow rate of the dry inert gas is 2-10L / min, and the mixing speed is 500-3500r / min.

[0043] Furthermore, before use, the polyol component is mixed and dissolved with 5-40% by volume of dry inert gas using a star-shaped mixing and stirring device. The dry inert gas is highly dispersed and dissolved in the polyol component, playing a key role in emulsifying the foam cells during the foaming process.

[0044] The polyol component contains countless physical foaming nucleation sites, which can stabilize the cells during the polyurethane reaction, making the cells finer and more uniform.

[0045] Furthermore, the gas may be air, carbon dioxide, nitrogen, or other inert gases.

[0046] Furthermore, the preparation method of the catalyst includes: adding the amine-tin catalyst to liquid paraffin at room temperature according to the formula ratio, mixing and stirring evenly to obtain the catalyst component.

[0047] Further, the preparation method of the isocyanate component includes: preparing raw materials according to the formula, dehydrating polytetrahydrofuran ether diol at 100-110℃ for 1.5-2h under a vacuum of 0.09-0.097MPa until the water content is less than 0.1%, mixing toluene diisocyanate with 40wt% polytetrahydrofuran ether diol at 75-90℃ for 1-2h to obtain B1; mixing diphenylmethane diisocyanate with 60wt% polytetrahydrofuran ether diol at 70-85℃ for 1-2h to obtain B2; mixing B1 and B2 with diphenylmethane diisocyanate and / or carbodiimide-modified diphenylmethane diisocyanate, mixing and reacting at 70-85℃ for 1-2h, and cooling to room temperature to obtain the isocyanate component.

[0048] Effective control of the molecular structure of isocyanate components allows the molecular chains of isocyanate components to exist in the form of highly regular PTMEG-TDI and PTMEG-MDI blocks or alone. When mixed and reacted with liquefied MDI-50, the isocyanate components can maintain low viscosity while ensuring a certain molecular weight and molecular chain regularity, resulting in better product performance.

[0049] The continuous preparation method of the above-mentioned polyurethane elastic pad includes the following steps:

[0050] S1. A premixed mixture of polyol and isocyanate components with a mass ratio of 100:70-100 is obtained after preheating. The preheating temperature of the polyol component is 45-70℃, and the preheating temperature of the isocyanate component is 35-55℃. Preheating can adjust the viscosity of the polyol and isocyanate components, improve the reaction activity, and facilitate high-pressure atomization and the initiation of reaction foaming.

[0051] S2. The premixed material is poured onto a horizontal steel strip through a sweeping frame, and the premixed material self-levels.

[0052] S3. Use flame or hot air to defoam the air bubbles on the surface of the leveled premixed material.

[0053] S4. The material after leveling and defoaming is then foamed and matured.

[0054] S5. After ripening, roll pressing is performed immediately, followed by traction and natural cooling;

[0055] S6. After traction and forming, the board is cut, packaged, stored, and then cured.

[0056] Furthermore, step S1 employs a high-pressure atomization collision method for mixing, with a nozzle diameter of 0.8-1.5 mm, a collision angle of 120-180°, and a pressure of 12-18 MPa. This setting enables more uniform mixing of the polyol component and the isocyanate component, and a more stable foaming reaction.

[0057] Furthermore, in step S3, the flame or hot air temperature is 200-300℃ and the hot air flow rate is 100-500L / min. This setting enables the physical bubbles generated on the surface after casting to break down quickly, resulting in a smoother product surface.

[0058] Furthermore, the conditions for the roller pressing in step S5 include: two pairs of upper and lower rollers pressing against each other, the gap between the upper and lower rollers being lower than the thickness of the pad, and the gap between the two rollers being 40-60% of the thickness of the pad; the traction speed being 0.5-3m / min, and natural cooling to 30-50℃.

[0059] Furthermore, the gap between the two rollers is 45-55% of the pad thickness. This preferred embodiment enables more stable cell structure and dimensions in the final product.

[0060] Furthermore, the curing temperature in step S4 is 50-80℃; the curing time in step S6 is 7-14 days. This setting can further improve the various performance characteristics of the product.

[0061] The working principle and beneficial effects of this invention are as follows:

[0062] 1. In this invention, the problem of uneven cell structure in the elastic pad is solved by the precise combination of polyol component and isocyanate component. At the same time, the polyurethane elastic pad has higher strength. The polyol component uses cell inducing agent and flow promoter. The two components work together to effectively improve the foaming effect, stabilize the cells, improve the fluidity of the mixture, and make the pad uniform and flat.

[0063] In this invention, the cell-inducing agent is primarily composed of inorganic nano-Al₂O₃ with surface-attached organic groups, allowing it to be uniformly dispersed within the polyol component. When mixed with the isocyanate component, it induces dissolved air within the system to form numerous bubble nuclei on its surface. As the reaction proceeds, more gas is generated, diffuses into the bubble nuclei, and continuously grows, leading to foaming and solidification. The main function of the cell-inducing agent is to attach the air mixed within the system to the nano-surface in the form of bubble nuclei. ， The gas generated after induction grows continuously around the bubble nucleus, resulting in a uniform and fine pore structure.

[0064] The flow promoter is based on polydimethylsiloxane and hexamethylene diisocyanate, with toluene as the solvent. The reaction produces organosilicon-modified polyurethane molecules. The ionic liquid 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate is used as the reactive solvent, which has better solubility and can dissolve organosilicon-modified polyurethane. At the same time, it can react with isocyanate. The resulting flow promoter has good compatibility with polyol components, can reduce the surface tension of the mixture, improve the flowability of the material, promote material leveling, eliminate the surface tension gradient between the inner and outer layers, and obtain a smooth pad surface.

[0065] 2. This invention involves preheating and mixing the polyol component and isocyanate component, then directly pouring the mixture onto the surface of a steel strip machine. After self-leveling and free foaming, the mixture is cured and molded before being cut into different sizes. This method offers high production efficiency, eliminates the need for molds, and allows for customized product dimensions. The method of using the polyol component involves dissolving a dry inert gas into it. This creates numerous physical foaming nucleation sites within the polyol component, which stabilize the cells during the polyurethane reaction, resulting in finer and more uniform pores.

[0066] 3. In the traditional preparation process of polyurethane elastic pads, the material mixing uniformity is poor, the cell structure is coarse, and the cells are large and unevenly distributed. When the pad is under stress, local stress concentration occurs inside, making it prone to breakage and resulting in low strength. This invention uses high-pressure atomization collision mixing, supplemented with cell inducing agents and flow promoters, which makes the material mixed uniformly, with fine and evenly distributed cells. Under stress, the cells are evenly distributed, without stress generation, and exhibit higher mechanical strength.

[0067] 4. This invention can significantly improve production efficiency; it can flexibly produce elastic pad products of different sizes; it can prepare elastic pads with a large width, such as 2.5m; and a long length, such as 30m; it is particularly suitable for producing elastic pads suitable for continuous laying; and the method of this invention can improve the problem of uneven cell structure of elastic pads.

[0068] The elastic pad prepared by the continuous preparation method of the present invention has advantages such as low density, low dynamic modulus ratio, high tensile strength and elongation, and the density of the obtained elastic pad is 300-500 kg / m³. 3 The static modulus is 0.05-1.0 N / mm. 3 The product width is 300-2500mm and the thickness is 10-30mm. Attached Figure Description

[0069] Figure 1 Here is an electron microscope image of the elastic pad material prepared in Example 3;

[0070] Figure 2 Here is an electron microscope image of the elastic pad material prepared in Example 4;

[0071] Figure 3 This is an electron microscope image of the elastic pad material prepared in Comparative Example 3. Detailed Implementation

[0072] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0073] In the following embodiments and comparative examples:

[0074] The polymer polyol is a mixture of polyether polyol and polytetrahydrofuran diol with a mass ratio of 7:3 and a number average molecular weight of 1000 with 2 functions.

[0075] Among them, the polytetrahydrofuran diol with 2 functions and a number average molecular weight of 1000 was purchased from BASF's PolyTHF 1000.

[0076] The polyether polyol is a mixture of polyether polyols with a functionality of 3000 number average molecular weight, a functionality of 5000 number average molecular weight, and a functionality of 6000 number average molecular weight in a mass ratio of 5:3:2.

[0077] Among them, the polyether polyol with 3000 number-average molecular weight and 3000 functionalities was purchased from Bluestar Dongda's EP3050.

[0078] The polyether polyol with 3 functionalities and a number-average molecular weight of 5000 was purchased from Bluestar Dongda EP330N.

[0079] The polyether polyol with 3 functionalities and a number-average molecular weight of 6000 was purchased from Bluestar Dongda's EP3600.

[0080] The hollow glass microspheres have a particle size of 20-500 μm and a bulk density of 0.3-0.4 g / cm³. 3 ;

[0081] Foaming agents M-8843, M-8804, M-8842, M-7771LF2, M-7738LF2, M-7731 and M-7730 were purchased from Jiangsu Meiside Chemical Co., Ltd.

[0082] The particle size of nano-Al2O3 is 100-1000 nm; preferably 200 nm.

[0083] The antioxidant is a mixture of antioxidant 1010 and ultraviolet absorber UV328 in a mass ratio of 2:1;

[0084] The chain extender is a mixture of a diol chain extender and a difunctional 400 molecular weight polyether polyol in a mass ratio of 6:4; wherein the difunctional 400 molecular weight polyether polyol was purchased from Bluestar Dongda's polyether 204.

[0085] The polybutadiene-acrylonitrile copolyol was purchased from Zibo Qilong Chemical Co., Ltd. as either HTBN-II or HTBN-III type.

[0086] The bis(hydroxyalkyl)-terminated polydimethylsiloxane was purchased from Anhui Aiyota Silicone Oil Co., Ltd., model IOTA2030-10, molecular weight 1000;

[0087] The bis(3-aminopropyl)-terminated polydimethylsiloxane was purchased from Hangzhou Sloan Materials Technology Co., Ltd., model SILONG 8100, molecular weight 1000.

[0088] Example 1

[0089] 1. Formula:

[0090] The raw materials consist of a polyol component and an isocyanate component in a mass ratio of 100:70;

[0091] The polyol component includes: 70 parts polymer polyol, 10 parts chain extender, 5 parts hollow glass microspheres, 0.1 parts foam stabilizer, 3 parts antioxidant, 0.5 parts cell inducing agent, 1 part flow promoter, and 0.5 parts catalyst.

[0092] The cell-inducing agent is prepared by reacting 50 parts of 3-isocyanate propyltrimethoxysilane, 10 parts of nano-Al2O3, and 30 parts of polybutadiene-acrylonitrile copolymer glycol. The specific preparation method includes the following steps: adding 50 parts of 3-isocyanate propyltrimethoxysilane to 50 parts of ethyl acetate, then uniformly adding 10 parts of nano-Al2O3 within 10 minutes, uniformly raising the temperature to 65 °C within 15 minutes, stirring at a stirring speed of 200 r / min, and reacting for 2 hours; then adding 30 parts of polybutadiene-acrylonitrile copolymer glycol, reacting for 6 hours, raising the temperature to 80 °C, and maintaining a vacuum degree of not less than 0.6 MPa, and distilling the ethyl acetate under reduced pressure to obtain the cell-inducing agent.

[0093] The flow promoter is prepared by reacting 50 parts of bis(hydroxyalkyl)-terminated polydimethylsiloxane, 15 parts of hexamethylene diisocyanate, 15 parts of 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate, 5 parts of diethylene glycol, and 30 parts of toluene. The specific preparation method includes the following steps: the bis(3-aminopropyl)-terminated polydimethylsiloxane is dehydrated at 80°C and a vacuum of not less than 0.8 MPa for 3 hours, then cooled to below 60°C. Hexamethylene diisocyanate is added, and the mixture is stirred at 70°C for 4 hours at a stirring speed of 200 r / min. Toluene is added and stirring is continued for 30 minutes. Then, diethylene glycol is added and stirring is continued for 2 hours. Finally, 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate is added and stirring is continued for 4 hours to obtain the flow promoter.

[0094] The chain extender is a mixture of a diol chain extender and a polyether polyol with a functionality of 400 in a mass ratio of 6:4.

[0095] The diol chain extender is neopentyl glycol monoester of hydroxypentyl acid;

[0096] The foaming agent is composed of component A and component B in a mass ratio of 8:2. Component A is selected from M-8843 of Jiangsu Meiside Chemical Co., Ltd., and component B is composed of M-7731 and M-7730 in a mass ratio of 1:1.

[0097] The particle size of the nano-Al2O3 is 100 nm;

[0098] The catalyst composition includes 40 wt% amine-tin catalyst and 60 wt% liquid paraffin;

[0099] The amine-tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2;

[0100] Organotin is stannous octoate.

[0101] The isocyanate component includes:

[0102] 40 parts of toluene diisocyanate (WANNATE TDI-80, Wanhua Chemical).

[0103] 20 parts of diphenylmethane diisocyanate (WANNATE MDI-100 from Wanhua Chemical).

[0104] 30 parts of diphenylmethane diisocyanate (WANNATE MDI-50 from Wanhua Chemical).

[0105] 10 parts of polytetrahydrofuran ether diol (BASF POLYTHF 1000).

[0106] 2. Component preparation process

[0107] 2.1 Catalyst Production Method

[0108] At room temperature, the amine-tin catalyst is added to liquid paraffin according to the formula ratio, and mixed evenly for 0.5 hours in a sealed environment. It is then sealed and stored for later use.

[0109] 2.2 Production methods of polyol components

[0110] Prepare the raw materials according to the formula, stir and disperse the polymer polyol, chain extender and antioxidant for 30 min at a stirring speed of 200 r / min, then grind until the fineness is less than 15 μm, then heat to 110℃ and continue stirring for 30 min; cool down to below 70℃, then add hollow glass microspheres, foam stabilizer, cell inducer, flow promoter and catalyst, continue mixing and stirring for 0.5 h, then adjust the water content to 0.25 wt% to obtain the polyol component.

[0111] 2.3 Production method of isocyanate component

[0112] Prepare the raw materials according to the formula. Dehydrate polytetrahydrofuran ether diol at 100℃ for 2 hours under a vacuum of 0.09MPa until the water content is less than 0.1%. Mix toluene diisocyanate with 40wt% polytetrahydrofuran ether diol at 90℃ for 1 hour to obtain B1. Mix diphenylmethane diisocyanate with 60wt% polytetrahydrofuran ether diol at 85℃ for 1 hour to obtain B2. Mix B1 and B2 with diphenylmethane diisocyanate and react at 85℃ for 1 hour. Cool to room temperature to obtain the isocyanate component.

[0113] 3. Material pretreatment

[0114] Before use, the polyol component is mixed with 40% by volume of dry inert gas, namely nitrogen, using a star-shaped mixing and stirring device. The mixing parameters are as follows: the polyol temperature is controlled at 35°C, the flow rate is 20 L / min, the dry inert gas flow rate is 2 L / min, and the mixing speed is 3500 r / min.

[0115] 4. Continuous forming process for elastic pads

[0116] 4.1 The polyol component and the isocyanate component with a mass ratio of 100:70 were preheated and mixed to obtain a premixed material; the preheating temperature of the isocyanate component was 35℃; the preheating temperature of the polyol component was 70℃; the mixing method was high-pressure atomization collision mixing, with a nozzle diameter of 0.8mm, a collision angle of 180°, and a pressure of 12MPa.

[0117] 4.2 The premixed material is poured onto a horizontal steel strip through a sweeping frame, and the premixed material self-levels;

[0118] 4.3 Hot air is used to defoam the air bubbles on the surface of the premixed material during leveling; the hot air temperature is 300℃ and the hot air flow rate is 100L / min.

[0119] 4.4 The material after leveling and defoaming is then foamed and matured; the maturation temperature is 80℃.

[0120] 4.5 After curing, roll pressing is performed immediately, followed by traction and natural cooling. The conditions for roll pressing include: two pairs of upper and lower rollers pressing against each other, the gap between the upper and lower rollers being less than the thickness of the pad, and the gap between the two rollers being 40% of the thickness of the pad; the traction speed is 3m / min, and natural cooling is performed to 30℃.

[0121] 4.6 After traction and forming, the boards are cut, packaged, stored, and then cured for 14 days.

[0122] Example 2

[0123] 1. Formula:

[0124] The raw materials consist of a polyol component and an isocyanate component in a mass ratio of 100:100;

[0125] The polyol component includes: 50 parts polymer polyol, 15 parts chain extender, 1 part hollow glass microspheres, 0.5 parts foam stabilizer, 0.5 parts antioxidant, 2 parts cell inducing agent, 0.1 parts flow promoter, and 3 parts catalyst.

[0126] The cell-inducing agent is prepared by reacting 30 parts of 3-isocyanate propyltrimethoxysilane, 40 parts of nano-Al2O3, and 20 parts of polybutadiene-acrylonitrile copolymer glycol. The specific preparation method includes the following steps: adding 30 parts of 3-isocyanate propyltrimethoxysilane to 80 parts of ethyl acetate, then uniformly adding 40 parts of nano-Al2O3 over 20 minutes, uniformly heating to 45°C over 15 minutes, stirring at a stirring speed of 200 r / min, and reacting for 3 hours; then adding 20 parts of polybutadiene-acrylonitrile copolymer glycol, reacting for 2 hours, heating to 100°C, maintaining a vacuum degree of not less than 0.6 MPa, and distilling the ethyl acetate under reduced pressure to obtain the cell-inducing agent.

[0127] The flow promoter is prepared by reacting 30 parts of bis(3-aminopropyl)-terminated polydimethylsiloxane, 30 parts of hexamethylene diisocyanate, 5 parts of 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate, 10 parts of diethylene glycol, and 10 parts of toluene. The specific preparation method includes the following steps: the bis(3-aminopropyl)-terminated polydimethylsiloxane is dehydrated at 100°C and a vacuum of not less than 0.8 MPa for 1 hour, then cooled to below 60°C. Hexamethylene diisocyanate is added, and the mixture is stirred at 95°C for 3 hours at a stirring speed of 200 r / min. Toluene is added and stirring is continued for 30 minutes. Then, diethylene glycol is added and stirring is continued for 3 hours. Finally, 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate is added and stirring is continued for 2 hours to obtain the flow promoter.

[0128] The chain extender is a mixture of a diol chain extender and a polyether polyol with a functionality of 400 in a mass ratio of 6:4.

[0129] The diol chain extender is 3-methyl-1,5-pentanediol;

[0130] The foaming agent is component A and component B in a mass ratio of 8:2. Component A is selected from M-8842 of Jiangsu Meiside Chemical Co., Ltd., and component B is M-7771LF2 and M-7738LF2 in a mass ratio of 1:1.

[0131] The particle size of the nano-Al2O3 is 1000 nm;

[0132] The catalyst composition includes 10 wt% amine-tin catalyst and 90 wt% liquid paraffin;

[0133] The amine-tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2;

[0134] Organotin is dibutyltin dilaurate.

[0135] The isocyanate component includes:

[0136] 30 parts of toluene diisocyanate (WANNATE TDI-80, Wanhua Chemical).

[0137] 25 parts of diphenylmethane diisocyanate (WANNATE MDI-100 from Wanhua Chemical).

[0138] 20 parts of carbodiimide-modified diphenylmethane diisocyanate (WANNATE CDMDI-100H).

[0139] 20 parts of polytetrahydrofuran ether diol (BASF POLYTHF 1000).

[0140] 2. Component preparation process

[0141] 2.1 Catalyst Production Method

[0142] At room temperature, the amine-tin catalyst is added to liquid paraffin according to the formula ratio, and mixed evenly for 0.5 hours in a sealed environment. It is then sealed and stored for later use.

[0143] 2.2 Production methods of polyol components

[0144] Prepare the raw materials according to the formula, stir and disperse the polymer polyol, chain extender and antioxidant for 30 min at a stirring speed of 200 r / min, then grind until the fineness is less than 15 μm, then heat to 105℃ and continue stirring for 30 min; cool down to below 70℃, then add hollow glass microspheres, foam stabilizer, cell inducer, flow promoter and catalyst, continue mixing and stirring for 1 h, then adjust the water content to 0.15 wt% to obtain the polyol component.

[0145] 2.3 Production method of isocyanate component

[0146] Prepare the raw materials according to the formula. Dehydrate polytetrahydrofuran ether diol at 110℃ for 1.5h under a vacuum of 0.097MPa until the water content is less than 0.1%. Mix toluene diisocyanate with 40wt% polytetrahydrofuran ether diol at 75℃ for 2h to obtain B1. Mix diphenylmethane diisocyanate with 60wt% polytetrahydrofuran ether diol at 70℃ for 2h to obtain B2. Mix B1 and B2 with or carbodiimide-modified diphenylmethane diisocyanate and mix and react at 70℃ for 2h. Cool to room temperature to obtain the isocyanate component.

[0147] 3. Material pretreatment

[0148] Before use, the polyol component is mixed with 5% by volume of dry inert gas, namely carbon dioxide, using a star-shaped mixing and stirring device. The mixing parameters are as follows: the polyol temperature is controlled at 55℃, the flow rate is 4L / min, the dry inert gas flow rate is 10L / min, and the mixing speed is 500r / min.

[0149] 4. Continuous forming process for elastic pads

[0150] 4.1 The polyol component and the isocyanate component with a mass ratio of 100:100 were preheated and mixed to obtain a premixed material; the preheating temperature of the isocyanate component was 55℃; the preheating temperature of the polyol component was 45℃; the mixing method was high-pressure atomization collision mixing, with a nozzle diameter of 1.5mm, a collision angle of 120°, and a pressure of 18MPa.

[0151] 4.2 The premixed material is poured onto a horizontal steel strip through a sweeping frame, and the premixed material self-levels;

[0152] 4.3 Hot air is used to defoam the air bubbles on the surface of the premixed material during leveling; the hot air temperature is 200℃ and the hot air flow rate is 500L / min.

[0153] 4.4 The material after leveling and defoaming is then foamed and matured; the maturation temperature is 50℃.

[0154] 4.5 After curing, roll pressing is performed immediately, followed by traction and natural cooling. The conditions for roll pressing include: two pairs of upper and lower rollers pressing against each other, the gap between the upper and lower rollers being less than the thickness of the pad, and the gap between the two rollers being 60% of the thickness of the pad; the traction speed is 0.5 m / min, and natural cooling is performed to 50℃.

[0155] 4.6 After traction and forming, the board is cut, packaged, stored, and then cured for 7 days.

[0156] Example 3

[0157] 1. Formula:

[0158] The raw materials consist of a polyol component and an isocyanate component in a mass ratio of 100:80;

[0159] The polyol component includes: 60 parts polymer polyol, 12 parts chain extender, 3 parts hollow glass microspheres, 0.3 parts foam stabilizer, 1 part antioxidant, 1 part cell inducing agent, 0.5 parts flow promoter, and 2 parts catalyst.

[0160] The cell-inducing agent is prepared by reacting 40 parts of 3-isocyanate propyltrimethoxysilane, 20 parts of nano-Al2O3, and 25 parts of polybutadiene-acrylonitrile copolymer glycol. The specific preparation method includes the following steps: 40 parts of 3-isocyanate propyltrimethoxysilane are added to 60 parts of ethyl acetate, followed by the uniform addition of 20 parts of nano-Al2O3 over 15 minutes. The temperature is then uniformly raised to 50 °C over 15 minutes, and the mixture is stirred at 200 r / min for 2.5 hours. Next, 25 parts of polybutadiene-acrylonitrile copolymer glycol are added, and after reacting for 5 hours, the temperature is raised to 90 °C under a vacuum of not less than 0.6 MPa. The ethyl acetate is then distilled under reduced pressure to obtain the cell-inducing agent.

[0161] The flow promoter is prepared by reacting 20 parts of bis(hydroxyalkyl)-terminated polydimethylsiloxane, 20 parts of bis(3-aminopropyl)-terminated polydimethylsiloxane, 20 parts of hexamethylene diisocyanate, 10 parts of 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate, 8 parts of diethylene glycol, and 15 parts of toluene. The specific preparation method includes the following steps: the bis(3-aminopropyl)-terminated polydimethylsiloxane and the bis(hydroxyalkyl)-terminated polydimethylsiloxane are dehydrated at 90°C and a vacuum degree of not less than 0.8 MPa for 2 hours, then the temperature is lowered to below 60°C. Hexamethylene diisocyanate is added, and the mixture is stirred at 80°C for 3.5 hours at a stirring speed of 200 r / min. Toluene is added and stirring is continued for 30 minutes. Then diethylene glycol is added and stirring is continued for 2.5 hours. Finally, 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate is added and stirring is continued for 3 hours to obtain the flow promoter.

[0162] The chain extender is a mixture of a diol chain extender and a polyether polyol with a functionality of 400 in a mass ratio of 6:4.

[0163] The diol chain extender is 1,4-dihydroxymethylcyclohexane;

[0164] The foaming agent is composed of component A and component B in a mass ratio of 8:2. Component A is selected from M-8804 of Jiangsu Meiside Chemical Co., Ltd., and component B is M-7771LF2.

[0165] The particle size of the nano-Al2O3 is 200 nm;

[0166] The catalyst composition includes 20 wt% amine-tin catalyst and 80 wt% liquid paraffin;

[0167] The amine-tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2;

[0168] Organotin is stannous octoate and dibutyltin dilaurate in a 1:1 mass ratio.

[0169] The isocyanate component includes:

[0170] 35 parts of toluene diisocyanate (WANNATE TDI-80, Wanhua Chemical).

[0171] 23 parts of diphenylmethane diisocyanate (WANNATE MDI-100 from Wanhua Chemical).

[0172] 20 parts of diphenylmethane diisocyanate (WANNATE MDI-50 from Wanhua Chemical).

[0173] Seven parts of carbodiimide-modified diphenylmethane diisocyanate (WANNATE CDMDI-100H).

[0174] 15 parts of polytetrahydrofuran ether diol (BASF POLYTHF 1000).

[0175] 2. Component preparation process

[0176] 2.1 Catalyst Production Method

[0177] At room temperature, the amine-tin catalyst is added to liquid paraffin according to the formula ratio, and mixed evenly for 0.5 hours in a sealed environment. It is then sealed and stored for later use.

[0178] 2.2 Production methods of polyol components

[0179] Prepare the raw materials according to the formula, stir and disperse the polymer polyol, chain extender and antioxidant for 30 min at a stirring speed of 200 r / min, then grind until the fineness is less than 15 μm, then heat to 108℃ and continue stirring for 30 min; cool down to below 70℃, then add hollow glass microspheres, foam stabilizer, cell inducer, flow promoter and catalyst, continue mixing and stirring for 1 h, then adjust the water content to 0.2 wt% to obtain the polyol component.

[0180] 2.3 Production method of isocyanate component

[0181] Prepare the raw materials according to the formula. Dehydrate polytetrahydrofuran ether diol at 105℃ for 2 hours under a vacuum of 0.095MPa until the water content is less than 0.1%. Mix toluene diisocyanate with 40wt% polytetrahydrofuran ether diol at 80℃ for 1.5 hours to obtain B1. Mix diphenylmethane diisocyanate with 60wt% polytetrahydrofuran ether diol at 80℃ for 1.5 hours to obtain B2. Mix B1 and B2 with diphenylmethane diisocyanate and carbodiimide-modified diphenylmethane diisocyanate, and mix and react at 80℃ for 1.5 hours. Cool to room temperature to obtain the isocyanate component.

[0182] 3. Material pretreatment

[0183] Before use, the polyol component is mixed with 10% by volume of dry inert gas using a star-shaped mixing and stirring device. The gas can be air, carbon dioxide, nitrogen, or other inert gas. The mixing parameters are as follows: the polyol temperature is controlled at 40°C, the flow rate is 10 L / min, the dry inert gas flow rate is 4 L / min, and the mixing speed is 1000 r / min.

[0184] 4. Continuous forming process for elastic pads

[0185] 4.1 The polyol component and the isocyanate component with a mass ratio of 100:80 were preheated and mixed to obtain a premixed material; the preheating temperature of the isocyanate component was 45℃; the preheating temperature of the polyol component was 50℃; the mixing method was high-pressure atomization collision mixing, with a nozzle diameter of 1.0mm, a collision angle of 150°, and a pressure of 15MPa.

[0186] 4.2 The premixed material is poured onto a horizontal steel strip through a sweeping frame, and the premixed material self-levels;

[0187] 4.3 Hot air is used to defoam the air bubbles on the surface of the premixed material during leveling; the hot air temperature is 250℃ and the hot air flow rate is 300L / min.

[0188] 4.4 The material after leveling and defoaming is then foamed and matured; the maturation temperature is 60℃.

[0189] 4.5 After curing, roll pressing is performed immediately, followed by traction and natural cooling. The conditions for roll pressing include: two pairs of upper and lower rollers pressing against each other, the gap between the upper and lower rollers being less than the thickness of the pad, and the gap between the two rollers being 50% of the thickness of the pad; the traction speed is 1m / min, and natural cooling is performed to 40℃.

[0190] 4.6 After traction and forming, the boards are cut, packaged, stored, and then cured for 10 days.

[0191] like Figure 1 This is an electron microscope image of the polyurethane elastic pad material prepared in this embodiment, showing a fine and uniform pore structure.

[0192] Example 4

[0193] 1. Formula:

[0194] The raw materials consist of a polyol component and an isocyanate component in a mass ratio of 100:80;

[0195] The polyol component includes: 60 parts polymer polyol, 12 parts chain extender, 3 parts hollow glass microspheres, 0.3 parts foam stabilizer, 1 part antioxidant, 1 part cell inducing agent, 0.5 parts flow promoter, and 2 parts catalyst.

[0196] The method for preparing the bubble inducing agent is the same as in Example 3;

[0197] The flow promoter is prepared by reacting 40 parts of bis(3-aminopropyl)-terminated polydimethylsiloxane, 20 parts of hexamethylene diisocyanate, 10 parts of 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate, 8 parts of diethylene glycol, and 15 parts of toluene. The specific preparation method includes the following steps: the bis(3-aminopropyl)-terminated polydimethylsiloxane is dehydrated at 90°C and a vacuum degree of not less than 0.8 MPa for 2 hours, then cooled to below 60°C. Hexamethylene diisocyanate is added, and the mixture is stirred at 80°C for 3.5 hours at a stirring speed of 200 r / min. Toluene is added and stirring is continued for 30 minutes. Then diethylene glycol is added and stirring is continued for 2.5 hours. Finally, 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate is added and stirring is continued for 3 hours to obtain the flow promoter.

[0198] The chain extender is a mixture of a diol chain extender and a polyether polyol with a functionality of 400 in a mass ratio of 6:4.

[0199] The diol chain extender is 1,4-dihydroxymethylcyclohexane;

[0200] The foaming agent is composed of component A and component B in a mass ratio of 8:2. Component A is selected from M-8804 of Jiangsu Meiside Chemical Co., Ltd., and component B is M-7771LF2.

[0201] The particle size of the nano-Al2O3 is 200 nm;

[0202] The catalyst composition includes 20 wt% amine-tin catalyst and 80 wt% liquid paraffin;

[0203] The amine-tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2;

[0204] Organotin is stannous octoate and dibutyltin dilaurate in a 1:1 mass ratio.

[0205] The isocyanate component includes:

[0206] 35 parts of toluene diisocyanate (WANNATE TDI-80, Wanhua Chemical).

[0207] 23 parts of diphenylmethane diisocyanate (WANNATE MDI-100 from Wanhua Chemical).

[0208] 20 parts of diphenylmethane diisocyanate (WANNATE MDI-50 from Wanhua Chemical).

[0209] Seven parts of carbodiimide-modified diphenylmethane diisocyanate (WANNATE CDMDI-100H).

[0210] 15 parts of polytetrahydrofuran ether diol (BASF POLYTHF 1000).

[0211] The component preparation process, material pretreatment, and continuous molding process of the elastic pad in steps 2-4 are the same as in Example 3.

[0212] like Figure 2 This is an electron microscope image of the polyurethane elastic pad material prepared in this embodiment, showing a relatively uniform pore structure.

[0213] Example 5

[0214] 1. Formula:

[0215] The raw materials consist of a polyol component and an isocyanate component in a mass ratio of 100:80;

[0216] The polyol component includes: 60 parts polymer polyol, 12 parts chain extender, 3 parts hollow glass microspheres, 0.3 parts foam stabilizer, 1 part antioxidant, 1 part cell inducing agent, 0.5 parts flow promoter, and 2 parts catalyst.

[0217] The method for preparing the bubble inducing agent is the same as in Example 3;

[0218] The flow promoter is prepared by reacting 40 parts of bis(hydroxyalkyl)-terminated polydimethylsiloxane, 20 parts of hexamethylene diisocyanate, 10 parts of 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate, 8 parts of diethylene glycol, and 15 parts of toluene. The specific preparation method includes the following steps: the bis(hydroxyalkyl)-terminated polydimethylsiloxane is dehydrated at 90°C and a vacuum degree of not less than 0.8 MPa for 2 hours, then cooled to below 60°C. Hexamethylene diisocyanate is added, and the mixture is stirred at 80°C for 3.5 hours at a stirring speed of 200 r / min. Toluene is added and stirring is continued for 30 minutes. Then diethylene glycol is added and stirring is continued for 2.5 hours. Finally, 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate is added and stirring is continued for 3 hours to obtain the flow promoter.

[0219] The chain extender is a mixture of a diol chain extender and a polyether polyol with a functionality of 400 in a mass ratio of 6:4.

[0220] The diol chain extender is 1,4-dihydroxymethylcyclohexane;

[0221] The foaming agent is composed of component A and component B in a mass ratio of 8:2. Component A is selected from M-8804 of Jiangsu Meiside Chemical Co., Ltd., and component B is M-7771LF2.

[0222] The particle size of the nano-Al2O3 is 200 nm;

[0223] The catalyst composition includes 20 wt% amine-tin catalyst and 80 wt% liquid paraffin;

[0224] The amine-tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2;

[0225] Organotin is stannous octoate and dibutyltin dilaurate in a 1:1 mass ratio.

[0226] The isocyanate component includes:

[0227] 35 parts of toluene diisocyanate (WANNATE TDI-80, Wanhua Chemical).

[0228] 23 parts of diphenylmethane diisocyanate (WANNATE MDI-100 from Wanhua Chemical).

[0229] 20 parts of diphenylmethane diisocyanate (WANNATE MDI-50 from Wanhua Chemical).

[0230] Seven parts of carbodiimide-modified diphenylmethane diisocyanate (WANNATE CDMDI-100H).

[0231] 15 parts of polytetrahydrofuran ether diol (BASF POLYTHF 1000).

[0232] The component preparation process, material pretreatment, and continuous molding process of the elastic pad in steps 2-4 are the same as in Example 3.

[0233] Comparative Example 1

[0234] 1. Formula:

[0235] The raw materials consist of a polyol component and an isocyanate component in a mass ratio of 100:80;

[0236] The polyol component includes: 60 parts polymer polyol, 12 parts chain extender, 3 parts hollow glass microspheres, 0.3 parts foam stabilizer, 1 part antioxidant, 0.5 parts flow promoter, and 2 parts catalyst.

[0237] The preparation method of the flow promoter is the same as in Example 3;

[0238] The chain extender is a mixture of a diol chain extender and a polyether polyol with a functionality of 400 in a mass ratio of 6:4.

[0239] The diol chain extender is 1,4-dihydroxymethylcyclohexane;

[0240] The foaming agent is composed of component A and component B in a mass ratio of 8:2. Component A is selected from M-8804 of Jiangsu Meiside Chemical Co., Ltd., and component B is M-7771LF2.

[0241] The particle size of the nano-Al2O3 is 200 nm;

[0242] The catalyst composition includes 20 wt% amine-tin catalyst and 80 wt% liquid paraffin;

[0243] The amine-tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2;

[0244] Organotin is stannous octoate and dibutyltin dilaurate in a 1:1 mass ratio.

[0245] The isocyanate component includes:

[0246] 35 parts of toluene diisocyanate (WANNATE TDI-80, Wanhua Chemical).

[0247] 23 parts of diphenylmethane diisocyanate (WANNATE MDI-100 from Wanhua Chemical).

[0248] 20 parts of diphenylmethane diisocyanate (WANNATE MDI-50 from Wanhua Chemical).

[0249] Seven parts of carbodiimide-modified diphenylmethane diisocyanate (WANNATE CDMDI-100H).

[0250] 15 parts of polytetrahydrofuran ether diol (BASF POLYTHF 1000).

[0251] 2. Component preparation process

[0252] 2.1 Catalyst Production Method

[0253] Same as Example 3.

[0254] 2.2 Production methods of polyol components

[0255] Prepare the raw materials according to the formula, stir and disperse the polymer polyol, chain extender and antioxidant for 30 minutes at a stirring speed of 200 r / min, then grind until the fineness is less than 15 μm, then heat to 108℃ and continue stirring for 30 minutes; cool down to below 70℃, then add hollow glass microspheres, foam stabilizer, flow promoter and catalyst, continue mixing and stirring for 1 hour, then adjust the water content to 0.2 wt% to obtain the polyol component.

[0256] 2.3 Production method of isocyanate component

[0257] Same as Example 3.

[0258] The material pretreatment and continuous molding process of the elastic pad in steps 3-4 are the same as in Example 3.

[0259] Comparative Example 2

[0260] 1. Formula:

[0261] The raw materials consist of a polyol component and an isocyanate component in a mass ratio of 100:80;

[0262] The polyol component includes: 60 parts polymer polyol, 12 parts chain extender, 3 parts hollow glass microspheres, 0.3 parts foam stabilizer, 1 part antioxidant, 1 part cell inducing agent, and 2 parts catalyst.

[0263] The method for preparing the bubble inducing agent is the same as in Example 3;

[0264] The chain extender is a mixture of a diol chain extender and a polyether polyol with a functionality of 400 in a mass ratio of 6:4.

[0265] The diol chain extender is 1,4-dihydroxymethylcyclohexane;

[0266] The foaming agent is composed of component A and component B in a mass ratio of 8:2. Component A is selected from M-8804 of Jiangsu Meiside Chemical Co., Ltd., and component B is M-7771LF2.

[0267] The particle size of the nano-Al2O3 is 200 nm;

[0268] The catalyst composition includes 20 wt% amine-tin catalyst and 80 wt% liquid paraffin;

[0269] The amine-tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2;

[0270] Organotin is stannous octoate and dibutyltin dilaurate in a 1:1 mass ratio.

[0271] The isocyanate component includes:

[0272] 35 parts of toluene diisocyanate (WANNATE TDI-80, Wanhua Chemical).

[0273] 23 parts of diphenylmethane diisocyanate (WANNATE MDI-100 from Wanhua Chemical).

[0274] 20 parts of diphenylmethane diisocyanate (WANNATE MDI-50 from Wanhua Chemical).

[0275] Seven parts of carbodiimide-modified diphenylmethane diisocyanate (WANNATE CDMDI-100H).

[0276] 15 parts of polytetrahydrofuran ether diol (BASF POLYTHF 1000).

[0277] 2. Component preparation process

[0278] 2.1 Catalyst Production Method

[0279] Same as Example 3.

[0280] 2.2 Production methods of polyol components

[0281] Prepare the raw materials according to the formula, stir and disperse the polymer polyol, chain extender and antioxidant for 30 min at a stirring speed of 200 r / min, then grind until the fineness is less than 15 μm, then heat to 108℃ and continue stirring for 30 min; cool down to below 70℃, then add hollow glass microspheres, foam stabilizer, foam inducing agent and catalyst, continue mixing and stirring for 1 h, then adjust the water content to 0.2 wt% to obtain the polyol component.

[0282] 2.3 Production method of isocyanate component

[0283] Same as Example 3.

[0284] The material pretreatment and continuous molding process of the elastic pad in steps 3-4 are the same as in Example 3.

[0285] Comparative Example 3

[0286] 1. Formula:

[0287] The raw materials consist of a polyol component and an isocyanate component in a mass ratio of 100:80;

[0288] The polyol component includes: 60 parts polymer polyol, 12 parts chain extender, 3 parts hollow glass microspheres, 0.3 parts foam stabilizer, 1 part antioxidant, and 2 parts catalyst.

[0289] The chain extender is a mixture of a diol chain extender and a polyether polyol with a functionality of 400 in a mass ratio of 6:4.

[0290] The diol chain extender is 1,4-dihydroxymethylcyclohexane;

[0291] The foaming agent is composed of component A and component B in a mass ratio of 8:2. Component A is selected from M-8804 of Jiangsu Meiside Chemical Co., Ltd., and component B is M-7771LF2.

[0292] The particle size of the nano-Al2O3 is 200 nm;

[0293] The catalyst composition includes 20 wt% amine-tin catalyst and 80 wt% liquid paraffin;

[0294] The amine-tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2;

[0295] Organotin is stannous octoate and dibutyltin dilaurate in a 1:1 mass ratio.

[0296] The isocyanate component includes:

[0297] 35 parts of toluene diisocyanate (WANNATE TDI-80, Wanhua Chemical).

[0298] 23 parts of diphenylmethane diisocyanate (WANNATE MDI-100 from Wanhua Chemical).

[0299] 20 parts of diphenylmethane diisocyanate (WANNATE MDI-50 from Wanhua Chemical).

[0300] Seven parts of carbodiimide-modified diphenylmethane diisocyanate (WANNATE CDMDI-100H).

[0301] 15 parts of polytetrahydrofuran ether diol (BASF POLYTHF 1000).

[0302] 2. Component preparation process

[0303] 2.1 Catalyst Production Method

[0304] Same as Example 3.

[0305] 2.2 Production methods of polyol components

[0306] Prepare the raw materials according to the formula, stir and disperse the polymer polyol, chain extender and antioxidant for 30 minutes at a stirring speed of 200 r / min, then grind until the fineness is less than 15 μm, then heat to 108℃ and continue stirring for 30 minutes; cool down to below 70℃, then add hollow glass microspheres, foam stabilizer and catalyst, continue mixing and stirring for 1 hour, then adjust the water content to 0.2 wt% to obtain the polyol component.

[0307] 2.3 Production method of isocyanate component

[0308] Same as Example 3.

[0309] The material pretreatment and continuous molding process of the elastic pad in steps 3-4 are the same as in Example 3.

[0310] like Figure 3This is an electron microscope image of the polyurethane elastic pad material prepared in this comparative example. The cell structure is rough and uneven.

[0311] Comparative Example 4

[0312] Compared with Example 3, the only difference is that step 3 - material pretreatment operation was not performed.

[0313] Comparative Example 5

[0314] Compared with Example 3, the only difference lies in step 4, the continuous molding process of the elastic pad:

[0315] 4.1 The polyol component and the isocyanate component with a mass ratio of 100:80 were preheated and mixed to obtain a premixed material; the preheating temperature of the isocyanate component was 45℃; the preheating temperature of the polyol component was 50℃; the mixing method was mechanical stirring at a stirring speed of 5000r / min.

[0316] The performance of the elastic pads prepared in Examples 1-5 and Comparative Examples 1-5 was tested according to the test methods in Table 1, and the results are shown in Tables 2-3.

[0317] Table 1 Test methods for polyurethane elastic pads

[0318]

[0319] Table 2 Performance parameters of polyurethane elastic pads in Examples 1-5

[0320]

[0321] Table 3 Performance parameters of polyurethane elastic pads in Comparative Examples 1-5

[0322]

[0323] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications or omissions made during the development of the present invention are subject to further clarification.

[0324] Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles should be included within the scope of protection of this invention.

Claims

1. A polyurethane elastomeric mat, characterized in that, The raw materials include polyol component and isocyanate component in a mass ratio of 100:70-100; The polyol component includes 50-70 parts of polymeric polyol, 10-15 parts of chain extender, 1-5 parts of hollow glass microbead, 0.1-0.5 parts of cell stabilizer, 0.5-3 parts of antioxidant, 0.5-2 parts of cell inducer, 0.1-1 parts of flow promoter and 0.5-3 parts of catalyst; The cell inducer is prepared by reacting 30-50 parts of 3-isocyanate propyl trimethoxysilane, 10-40 parts of nano Al2O3 and 20-30 parts of polybutadiene-acrylonitrile copolymer diol; The flow promoter is prepared by reacting 30-50 parts of hydroxyl-terminated and / or amino-terminated polydimethylsiloxane, 15-30 parts of hexamethylene diisocyanate, 5-15 parts of 1-hydroxyethyl-3-methyl imidazole tetrafluoroborate, 5-10 parts of diethylene glycol and 10-30 parts of toluene; The polymeric polyol is selected from polyols with a number average molecular weight of 1000-6000 and a functionality of 2 or 3; Before use, the polyol component is mixed into 5-40% volume percentage of dry inert gas; wherein the parameters during mixing are as follows: the temperature of the polyol is controlled to be 35-55℃, the flow rate is 4-20 L / min, the flow rate of the dry inert gas is 2-10 L / min, and the mixing rotation speed is 500-3500 r / min; The polyol component and the isocyanate component in the raw materials are mixed by high-pressure atomization and collision, the nozzle diameter is 0.8-1.5 mm, the collision angle is 120-180°, and the pressure is 12-18 MPa.

2. A polyurethane elastomeric backing plate according to claim 1, wherein, The preparation method of the cell inducer includes the following steps: 30-50 parts of 3-isocyanate propyl trimethoxysilane is added into 50-80 parts of ethyl acetate, then 10-40 parts of nano Al2O3 is uniformly added within 10-20 minutes, the temperature is raised to 45-65℃, stirring is performed, and reaction is performed for 2-3 h; then 20-30 parts of polybutadiene-acrylonitrile copolymer diol is added, reaction is performed for 2-6 h, the temperature is raised to 80-100℃, the vacuum degree is not less than 0.6 MPa, the ethyl acetate is distilled under reduced pressure, and the cell inducer is obtained.

3. The polyurethane resilient mat of claim 1, wherein, The preparation method of the flow promoter includes the following steps: bis(3-aminopropyl)-terminated polydimethylsiloxane and / or bis(hydroxyalkyl)-terminated polydimethylsiloxane is dehydrated at 80-100℃ and a vacuum degree of not less than 0.8 MPa for 1-3 h, the temperature is reduced to below 60℃, hexamethylene diisocyanate is added, stirring is performed at 70-95℃ for 3-4 h, toluene is added and stirring is continued for 30 min, then diethylene glycol is added, stirring is continued for 2-3 h, finally 1-hydroxyethyl-3-methyl imidazole tetrafluoroborate is added, stirring is continued for 2-4 h, and the flow promoter is obtained.

4. The polyurethane resilient mat of claim 1, wherein, The polymeric polyol is a mixture of polyether polyol and 2-functionality 1000 number average molecular weight polytetrahydrofuran diol in a mass ratio of 7:

3. The polyether polyol is a mixture of 3-functional 3000 number average molecular weight, 3-functional 5000 number average molecular weight and 3-functional 6000 number average molecular weight polyether polyols in a mass ratio of 5:3:2; The chain extender is a mixture of a diol chain extender and a 2-functional 400 number average molecular weight polyether polyol in a mass ratio of 6:4; The diol chain extender is selected from a mixture of one or more of hydroxypivalyl hydroxypivalate, 3-methyl-1,5-pentanediol and 1,4-dimethylolcyclohexane; The hollow glass microsphere has a particle size of 20-500 μm and a bulk density of 0.3-0.4 g / cm 3 ; The cell uniformizer is selected from a mixture of one or more of M-8843, M-8804, M-8842, M-7771LF2, M-7738LF2, M-7731 and M-7730 of Jiangsu Meishide Chemical Co., Ltd.; The antioxidant is a mixture of antioxidant 1010 and ultraviolet absorber UV328 in a mass ratio of 2:1; The nano-Al2O3 has a particle size of 100-1000 nm; The catalyst component comprises 10-40 wt% amine tin catalyst and 60-90 wt% liquid paraffin; the amine tin catalyst is a mixture of organotin and amine catalyst A33 in a mass ratio of 1:2; the organotin is stannous octoate and / or dibutyltin dilaurate.

5. The polyurethane resilient mat of claim 1, wherein, The isocyanate component comprises: 30-40 parts of toluene diisocyanate, 20-25 parts of methylene dianiline diisocyanate, 20-30 parts of methylene dianiline diisocyanate and / or carbodiimide modified methylene dianiline diisocyanate, 10-20 parts of polytetrahydrofuran ether diol.

6. The polyurethane resilient mat of claim 1, wherein, The preparation method of the polyol component comprises: preparing raw materials according to the formula, stirring and mixing the polymeric polyol, chain extender and antioxidant for 30 min, then grinding to a fineness of less than 15 μm, then heating to 105-110°C, and continuing to stir for 30 min; cooling to below 70°C, then adding hollow glass microbeads, cell uniformizer, cell inducing agent, flow promoter and catalyst, and continuing to mix and stir for 0.5-1 h, then adjusting the water content to 0.15-0.25 wt% to obtain the polyol component.

7. A polyurethane resilient mat according to claim 1, wherein The preparation method of the isocyanate component comprises: preparing raw materials according to the formula, dehydrating polytetrahydrofuran ether diol at 100-110°C for 1.5-2 h under a vacuum degree of 0.09-0.097 MPa until the water content is less than 0.1%, mixing toluene diisocyanate with 40 wt% polytetrahydrofuran ether diol at 75-90°C for 1-2 h to obtain B1; mixing methylene dianiline diisocyanate with 60 wt% polytetrahydrofuran ether diol at 70-85°C for 1-2 h to obtain B2; mixing B1, B2, methylene dianiline diisocyanate and / or carbodiimide modified methylene dianiline diisocyanate at 70-85°C for 1-2 h, and cooling to room temperature to obtain the isocyanate component.

8. A continuous process for the production of polyurethane resilient floor underlay as claimed in claim 1, characterised in that, The method comprises the following steps: S1, the polyol component and the isocyanate component with a mass ratio of 100:70-100 are mixed after preheating to obtain a premix; wherein the preheating temperature of the polyol component is 45-70℃, and the preheating temperature of the isocyanate component is 35-55℃; S2, the premix is poured on a horizontal steel belt through a horizontal sweeping frame, and the premix is self-leveling; S3, hot air is used to defoam the bubbles on the surface of the leveled premix; S4, the defoamed and leveled material is foamed and cured; S5, after curing, the material is immediately rolled, then pulled and naturally cooled; S6, after the material is cut, packaged, stored and post-cured.

9. A continuous process for the production of polyurethane resilient floor underlay according to claim 8, characterised in that, The hot air temperature in step S3 is 200-300℃, and the hot air flow is 100-500L / min; The rolling conditions in step S5 include: two pairs of upper and lower rollers are used for pressing, the gap between the upper and lower rollers is lower than the thickness of the pad, the gap between the double rollers is 40-60% of the thickness of the pad; the pulling speed is 0.5-3m / min, and the natural cooling is to 30-50℃; The curing temperature in step S4 is 50-80℃; the post-curing time in step S6 is 7-14 days.

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