High-performance carbon dioxide-based polyurethane foam and preparation method thereof
High-performance polyurethane foams were prepared by combining carbon dioxide-based polyols with specific polyether polyols, optimizing the isocyanate index and additives, solving the problems of petroleum dependence and performance balance, and optimizing softness, compression set and resilience, thus promoting the application of carbon dioxide-based polyols in the polyurethane industry.
Patent Information
- Application Number
- CN202511740951.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-25
- Publication Date
- 2026-01-27
AI Technical Summary
Existing polyurethane foam materials are heavily reliant on petroleum resources and struggle to balance properties such as softness, elasticity, and compressibility. The introduction of carbonate structural units affects foam performance, necessitating optimization of component synergy.
High-performance polyurethane foam is prepared by replacing part of the petroleum-based polyether polyol with carbon dioxide-based polyol, combining polyether polyols with specific molecular weights and structures, achieving an isocyanate index of 0.9, and using silicone oil surfactants, cell openers, catalysts, etc., through mixing and foaming reactions.
High-performance polyurethane foams with softness, fine texture, suitable recovery time, and low compression deformation are prepared, which are suitable for mattresses, cushions and other fields, and promote the application of carbon dioxide-based polyols in the polyurethane industry.
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Figure CN121405899A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polyurethane technology, and in particular to a high-performance carbon dioxide-based polyurethane foam and its preparation method. Background Technology
[0002] Polyurethane foam is one of the most important polymer materials currently available. Its greatest advantage lies in its ability to flexibly adjust the performance of the final product by changing the raw materials and formulation, thereby meeting various needs from ultra-soft to high-rigidity. Soft, slow-rebound polyurethane foam is mostly semi-closed-cell and semi-open-cell structure, possessing excellent compression resistance, cushioning, and comfort characteristics. It can be widely used in mattresses, pillows, toys, clothing linings, cushioning packaging, and other fields. The main raw material of traditional polyurethane—polyether / polyester polyol—is mostly derived from petroleum, which makes the development of the polyurethane industry heavily constrained by petroleum resources.
[0003] Carbon dioxide-based polyols are oligomeric polyols copolymerized from carbon dioxide and epoxides under the action of a catalyst. Their molecular chain structure is a combination of repeating structural units of carbonate and ether bonds, with active hydroxyl groups located at the end groups. They can replace polyether or polyester polyols in the synthesis of carbon dioxide-based polyurethanes, which can reduce the dependence of the polymer industry on petroleum resources and is of great significance for the diversification of raw material sources and sustainable development of the polymer industry.
[0004] Carbon dioxide-based polyols can be seen as polyether polyols modified with carbonate structures, combining the advantages of both polyether polyols and polycarbonate polyols. However, due to the large cohesive energy and strong molecular chain rigidity of carbonate structural units, the presence of carbonate structural units will also affect the elasticity, softness and other properties of polyurethane foam. Therefore, to prepare polyurethane foam with good comprehensive performance, it is necessary to select and formulate other components to cooperate with each other. Summary of the Invention
[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a high-performance carbon dioxide-based polyurethane foam that uses carbon dioxide-based polyols to replace part of the petroleum-based polyether polyols, as well as a method for preparing the polyurethane foam.
[0006] This invention is achieved through the following technical solution: A high-performance carbon dioxide-based polyurethane foam, wherein the polyurethane foam is a soft, slow-rebound foam with a density of 35-45 kg / m³. 3The 40% compression load is 2.2-2.8 kPa, the recovery time is 2-8 seconds, and the permanent deformation at 75% compression is ≤10%. Compared to conventional polyurethane slow rebound foam, the carbon dioxide-based polyurethane foam of this invention is softer, has finer pores, a suitable recovery time, and less compression deformation, making it a compression-resistant polyurethane slow rebound foam product. If the recovery time is too short, the slow rebound effect is not achieved, resulting in poor shape memory and a poor feel; if the recovery time is too long, it is difficult to provide a snug fit and support, leading to lower comfort.
[0007] Further, the polyurethane foam is prepared from the following raw materials in parts by weight: 30-60 parts of polyether polyol A, 5-30 parts of polyether polyol B, 5-25 parts of polyether polyol C, 10-50 parts of carbon dioxide-based polyol, 1.0-2.0 parts of silicone oil surfactant, 1.0-5.0 parts of cell opener, 1.5-5.0 parts of chemical foaming agent, 0.15-0.30 parts of amine catalyst, 0.05-0.20 parts of tin catalyst, 1-5 parts of chain extender, and 38-42 parts of toluene diisocyanate (TDI); wherein the isocyanate index is 0.80-0.95. The polyether polyol A has a molecular weight of 500-800, a hydroxyl value of 200-300 mg KOH / g, a theoretical functionality of 3.0-3.5, an EO content of 0%-5%, and a PO content of 80%-90%. The polyether polyol B has a molecular weight of 2500-3500, a hydroxyl value of 50-60 mg KOH / g, a theoretical functionality of 3.0, an EO content of 5%-13%, and a PO content of 85%-92%. The polyether polyol C has a molecular weight of 4000-5000, a hydroxyl value of 30-50 mg KOH / g, a theoretical functionality of 3.0, an EO content of 65%-80%, and a PO content of 20%-40%. The carbon dioxide-based polyol has a molecular weight of 2000-4000, a hydroxyl value of 28-56 mg KOH / g, a theoretical functionality of 2.0, a carbon dioxide content of 20-30%, and a PO content of 65%-75%.
[0008] Furthermore, the polyether polyol A uses glycerol and pentaerythritol as initiators and mainly uses propylene oxide as the polymerization monomer, containing little or no ethylene oxide (EO); the polyether polyol B and polyether polyol C are both copolymerized using glycerol as an initiator and ethylene oxide and propylene oxide as monomers, with polyether polyol B being a polyether polyol with high propylene oxide (PO) content and polyether polyol C being a polyether polyol with high ethylene oxide (EO) content.
[0009] The composition and structure of polyols that react with NCO groups directly affect the preparation and properties of polyurethane foams, such as their ability to foam, foam stability, cell structure, foam softness, compression set, compressive strength, and tensile strength. Studies have found that a single polyol often cannot balance multiple properties to meet various requirements, necessitating the synergistic combination of multiple polyols, especially with carbon dioxide-based polyols containing active hydroxyl groups. This requires considering the influence of carbonate and ether bonds in the carbon dioxide-based polyols through molecular design.
[0010] The properties of polyether polyols are closely related to their molecular structure. Their EO / PO content, molecular weight and distribution, functionality, hydroxyl value, etc., affect the foaming stability, softness, compression set, strength, etc. of polyurethane foam.
[0011] In this invention, polyether polyols B and C are both selected using glycerol as an initiator to control their functionality and hydroxyl value within a suitable range. Polyether polyol A, on the other hand, uses glycerol and pentaerythritol as initiators, allowing for a more appropriate increase in functionality to ensure that the reactivity, foam hardness, strength, and resilience meet the requirements. The polyether polyol composition primarily uses ethylene oxide (EO) and propylene oxide (PO) as comonomers to achieve good overall foam performance. Controlling their ratio is crucial; a higher EO ratio results in softer foam, but excessive EO can lead to poor compression set, low mechanical strength, and even poor stability during molding, potentially causing foam collapse. Therefore, their ratio should be controlled, and the optimal performance combination can be achieved through the synergistic effect of the various polyether polyols. Similarly, the molecular weight of the polyols directly affects the foam's resilience, strength, and hardness.
[0012] The isocyanate index directly affects the cell morphology, mechanical properties, and processing characteristics of polyurethane foam. A low isocyanate index results in slow foam rebound, reduced durability, and uneven cell structure; a high isocyanate index leads to stiffness, closed cells, and even shrinkage. Generally, the isocyanate index of slow-rebound polyurethane foam is controlled within the range of 80-95%. However, through multiple experiments and analyses, this invention found that an isocyanate index of around 0.9 is necessary to achieve the optimal preparation conditions for the polyurethane foam's performance characteristics (density, cell structure, softness, and resilience). This may be due to the influence of the addition of carbon dioxide-based polyols and the synergistic effects between various polyether polyols and their corresponding chain extenders.
[0013] A further preferred embodiment is that the carbon dioxide-based polyol is a polypropylene carbonate polyol containing both carbonate bonds and ether bonds within its molecule. The raw materials for its preparation include carbon dioxide, an initiator, an epoxide, and a catalyst. The epoxide is one or a combination of several of ethylene oxide, propylene oxide, 1,2-epoxybutane, epichlorohydrin, and condensed glycerol.
[0014] Furthermore, the initiator is one or a combination of several of ethylene glycol, diethylene glycol, 1,3-propanetriol, 1,2-propanediol, and 1,4-butanediol. Furthermore, the epoxide is propylene oxide.
[0015] Furthermore, the initiator is 1,2-propanediol.
[0016] Furthermore, the mass ratio of 1,2-propanediol, carbon dioxide, and propylene oxide is 1:(5-16):(15-45).
[0017] Initiators are crucial factors influencing the preparation process and reactivity of carbon dioxide-based polyols. The choice of initiator significantly impacts reaction activity, selectivity, and the content, molecular weight, and distribution of carbonate units in the product. As a component replacing some petroleum-based polyether polyols, the reactivity of carbon dioxide-based polyols directly affects their conversion rate and the final polyurethane foam performance. This reactivity is directly related to the hydroxyl structure at the molecular chain ends. The type and amount of initiator directly affect the reaction process and the product's reactivity. Different initiators have different structures and hydroxyl reactivity, leading to variations in reactivity and product properties. The functionality of the initiator directly determines the functionality of the carbon dioxide-based polyol; a lower functionality reduces foam durability and resilience, while a higher functionality results in a poorer feel and stiffer foam.
[0018] The present invention selects 1,2-propanediol as the preferred initiator, which can achieve a better balance in terms of reaction time, molecular weight distribution of products, reactivity, and cost.
[0019] More preferably, the chain extender is 1,4 The combination of butanediol and PEG200, 1,4 The mass ratio of butanediol to PEG200 is 1:(0.2-0.5). This invention uses 1,4... Butylene glycol and PEG200 are chain extenders. PEG200 has a soft molecular chain and moderate reactivity, which can improve the chain extension properties of 1,4-butanediol and PEG200. The defects of butylene glycol single chain extender, such as excessively fast reaction rate and excessively hard chain segments, can be balanced in terms of reaction rate control and product molecular chain flexibility. This makes the reaction rate controllable and can further improve the tensile strength, tear resistance and compression resistance of foam products while ensuring their softness and resilience.
[0020] More preferably, the cell-opening agent includes a first cell-opening agent and a second cell-opening agent. The first cell-opening agent is a polyether polyol-based soft slow-rebound foam cell-opening agent, suitable for slow-rebound foam sponges, which can effectively improve the open cell ratio of the foam, improve the foam structure, and give the product excellent comfort, a smooth feel, and fine pores. The second cell-opening agent is a slow-rebound cell-opening agent emulsion, which can effectively prevent the shrinkage of the sponge foam product, while also making the foam soft and having a very good feel, and the product has fine pores.
[0021] Silicone oil surfactants play a role in homogenizing and stabilizing foams during polyurethane foaming, adjusting the porosity to make the cells finer and more uniform. A further preferred embodiment is that the silicone oil surfactant is flexible foam slow-rebound silicone oil B8002 or / and flexible foam slow-rebound silicone oil L-838. Evonik B8002 is suitable for high-density foams and polyurethane formulations containing high-efficiency polyols. Compared with conventional silicone oils, it allows for the use of higher concentrations of tin catalysts, reducing the tendency for foam cracking or shrinkage. Momentive L-838 can adapt to a wide range of sponge formulations in terms of density, providing greater process tolerance and significantly improving foam stability.
[0022] A further preferred embodiment is that the amine catalyst is triethylenediamine, which belongs to the category of gelling amine catalysts; and the tin catalyst is stannous neodecanoate. The combination of these two catalysts can achieve high catalytic activity and realize a balance between the curing and foaming processes.
[0023] A further preferred embodiment is that the chemical foaming agent is water.
[0024] A method for preparing the above-mentioned high-performance carbon dioxide-based polyurethane foam includes the following steps: The first component is obtained by uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, chain extender, etc., in stoichiometric amounts. At room temperature and a rotation speed of 2000-4000 rpm, stoichiometric amounts of toluene diisocyanate are added to the first component. After mixing and reacting for 3-8 seconds, the mixture is injected into a box mold at room temperature or a closed mold at 40-80℃ for foaming reaction for 2-10 minutes. After curing, carbon dioxide-based polyurethane foam is obtained.
[0025] This invention designs the structure, properties, and raw materials of carbon dioxide-based polyols to obtain polypropylene carbonate polyols suitable for slow-rebound polyurethane foams. It also selects polyether polyols A, B, and C with suitable structural characteristics to combine with these polyether polyols. Furthermore, through the selection of combinations of silicone oil surfactants, cell openers, and chain extenders, the resulting carbon dioxide-based polyurethane flexible foam exhibits excellent comprehensive properties, demonstrating good performance in resilience, compression set, and tensile strength. It can be used in cushions, seat cushions, mattresses, and other fields, promoting the replacement of petroleum-based polyether polyols in the polyurethane industry and having a positive impact on the comprehensive utilization of resources. Detailed Implementation
[0026] A high-performance carbon dioxide-based polyurethane foam, wherein the polyurethane foam is a soft, slow-rebound foam with a density of 35-45 kg / m³. 3 40% compression load is 2.2-2.8 kPa, recovery time is 2-8 s, and 75% compression set is ≤10%.
[0027] The polyurethane foam with the above-mentioned performance characteristics is prepared from the following raw materials in parts by weight: 30-60 parts of polyether polyol A, 5-30 parts of polyether polyol B, 5-25 parts of polyether polyol C, 10-50 parts of carbon dioxide-based polyol, 1.0-2.0 parts of silicone oil surfactant, 1.0-5.0 parts of cell opener, 1.5-5.0 parts of chemical foaming agent, 0.15-0.30 parts of amine catalyst, 0.05-0.20 parts of tin catalyst, 1-5 parts of chain extender, and 38-42 parts of toluene diisocyanate (TDI); wherein the isocyanate index is 0.80-0.95.
[0028] The polyether polyol A has a molecular weight of 500-800, a hydroxyl value of 200-300 mg KOH / g, a theoretical functionality of 3.0-3.5, an EO content of 0%-5%, and a PO content of 80%-90%. The polyether polyol B has a molecular weight of 2500-3500, a hydroxyl value of 50-60 mg KOH / g, a theoretical functionality of 3.0, an EO content of 5%-13%, and a PO content of 85%-92%. The polyether polyol C has a molecular weight of 4000-5000, a hydroxyl value of 30-50 mg KOH / g, a theoretical functionality of 3.0, an EO content of 65%-80%, and a PO content of 20%-40%. The carbon dioxide-based polyol has a molecular weight of 2000-4000, a hydroxyl value of 28-56 mg KOH / g, a theoretical functionality of 2.0, a carbon dioxide content of 20-30%, and a PO content of 65%-75%.
[0029] In some embodiments, the polyether polyol A uses glycerol and pentaerythritol as initiators and propylene oxide as the main polymerizing monomer, and contains little or no ethylene oxide (EO); the polyether polyol B and polyether polyol C are both copolymerized using glycerol as an initiator and ethylene oxide and propylene oxide as monomers, with polyether polyol B being a polyether polyol with high propylene oxide (PO) content and polyether polyol C being a polyether polyol with high ethylene oxide (EO) content.
[0030] In some embodiments, the carbon dioxide-based polyol is a polyether carbonate polyol containing both carbonate and ether bonds within its molecule. Its preparation raw materials include carbon dioxide, an initiator, an epoxide, and a catalyst. The epoxide is one or a combination of several of ethylene oxide, propylene oxide, 1,2-epoxybutane, epichlorohydrin, and condensed glycerol.
[0031] In some embodiments, the specific method is that the carbon dioxide-based polyol is a polypropylene carbonate polyol, a novel polycarbonate polyol containing both carbonate bonds and ether bonds within its molecule. Its preparation raw materials include the following components: initiator, propylene oxide, and carbon dioxide, wherein the mass ratio of the initiator, carbon dioxide, and propylene oxide is 1:(5-16):(15-45). The initiator is preferably 1,2-propanediol.
[0032] In some embodiments, the chain extender is 1,4 The combination of butanediol and PEG200, 1,4 The mass ratio of butanediol to PEG200 is 1:(0.2-0.5).
[0033] In some embodiments, the cell-opening agent includes a first cell-opening agent and a second cell-opening agent. The first cell-opening agent is a polyether polyol-based soft slow-rebound foam cell-opening agent, suitable for slow-rebound foam sponges, which can effectively improve the open cell ratio of the foam, improve the foam structure, and give the product excellent comfort, a smooth feel, and fine pores. The second cell-opening agent is a slow-rebound cell-opening agent emulsion, which can effectively prevent the shrinkage of the foam product, while also making the foam soft and having a very good feel, and the product has fine pores.
[0034] In some embodiments, the silicone oil surfactant is flexible foam slow-rebound silicone oil B8002 or / and flexible foam slow-rebound silicone oil L-838. Evonik B8002, compared to conventional silicone oils, allows for the use of higher concentrations of tin catalysts, reducing the tendency for foam cracking or shrinkage, while Momentive L-838 provides a wider process tolerance, significantly improving foam stability and open-cell structure.
[0035] In some embodiments, the amine catalyst is triethylenediamine, which belongs to the category of gelling amine catalysts; the tin catalyst is stannous neodecanoate. The combination of these two catalysts achieves high catalytic activity, realizing a balance between the curing and foaming processes. For chemical foaming agents, water is preferred.
[0036] A method for preparing the above-mentioned high-performance carbon dioxide-based polyurethane foam includes the following steps: The stoichiometric amounts of polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, chain extender, etc. are mixed evenly to obtain the first component. At room temperature and a rotation speed of 2000-4000 rpm, stoichiometric amounts of toluene diisocyanate are added to the first component. After mixing and reacting for 3-8 seconds, the mixture is injected into a box mold at room temperature or a closed mold at 40-80℃ for foaming reaction for 2-10 minutes to obtain carbon dioxide-based polyurethane foam.
[0037] Example 1 The raw material composition of a high-performance carbon dioxide-based polyurethane foam is as follows: 50 parts of polyether polyol A, 20 parts of polyether polyol B, 10 parts of polyether polyol C, 20 parts of carbon dioxide-based polyol, 1.4 parts of silicone oil surfactant, 3 parts of cell opener, 2.2 parts of chemical foaming agent, 0.18 parts of amine catalyst, 0.06 parts of tin catalyst, 3.5 parts of chain extender, 40.17 parts of toluene diisocyanate, and an isocyanate index of 90.
[0038] Among them, polyether polyol A is Shell's GB250-200 product, which is copolymerized with glycerol and pentaerythritol as initiators and ethylene oxide and propylene oxide as monomers. Its molecular weight is 670, hydroxyl value is 250 mg KOH / g, PO content is 86%, and it does not contain EO.
[0039] Among them, the polyether polyol B is the SC56-16S product of CNOOC Shell Petrochemical Co., Ltd., which is copolymerized with glycerol as the initiator and ethylene oxide and propylene oxide as monomers. It has a molecular weight of 3000, a hydroxyl value of 56 mg KOH / g, a PO content of 89%, and an EO content of 8%.
[0040] Among them, the polyether polyol C is the SA36-18K product of CNOOC Shell Petrochemical Co., Ltd., which is copolymerized with glycerol as the initiator and ethylene oxide and propylene oxide as monomers. It has a molecular weight of 4700, a hydroxyl value of 36mg KOH / g, a PO content of 26%, and an EO content of 72%.
[0041] Among them, the carbon dioxide-based polyol is the PPCD222 product of Dazhi Fine Chemical Co., Ltd., with 1,2-propanediol as the initiator, a molecular weight of 2000, a hydroxyl value of 56 mg KOH / g, propylene oxide and carbon dioxide as comonomers, carbon dioxide content of 28%, and propylene oxide PO content of 68%.
[0042] The silicone oil surfactant is a combination of flexible foam slow-rebound silicone oil B8002 and flexible foam slow-rebound silicone oil L-838, with a mass ratio of 1:1. Flexible foam slow-rebound silicone oil B8002 is the Evonik B8002 product from Germany, and flexible foam slow-rebound silicone oil L-838 is the Niax L-838 product from Momentive.
[0043] The cell opener includes a first cell opener and a second cell opener. The first cell opener is a special polyether polyol (cell opener) product of Korean SKC Y-1900, and the second cell opener is a cell opener emulsion of Huaian Bad BDM-4. The mass ratio of the two is 1:1.3.
[0044] The physical foaming agent is deionized water.
[0045] The amine catalyst used is Momentive A-33, which is a mixed solution of 33% by weight triethylenediamine and 67% by weight dipropylene glycol (DPG).
[0046] The tin-based catalyst used is Momentive D-25, which is composed of stannous neodecanoate.
[0047] The chain extender is 1,4 The combination of butanediol and PEG200, with a mass ratio of 1:0.3, uses 1,4-butanediol from BASF and PEG200 from Dow Chemical.
[0048] Toluene diisocyanate was selected from BASF's TDI-80 product.
[0049] A method for preparing high-performance carbon dioxide-based polyurethane foam includes the following steps: The first component is obtained by uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, chain extender, etc., in stoichiometric amounts. At room temperature (23℃) and a rotation speed of 3000 rpm, stoichiometric amounts of toluene diisocyanate were added to the first component. After mixing thoroughly for 5 seconds, the mixture was injected into a mold at room temperature for foaming reaction for 5 minutes and then cured for 45 minutes to obtain carbon dioxide-based polyurethane foam.
[0050] The obtained carbon dioxide-based polyurethane foam was a flexible foam, and tests were conducted on its density, resilience, and strength. Specifically, its density, 40% compression load, recovery time, tensile strength, elongation at break, tear strength, and 75% compression set were tested. The testing methods for each indicator were as follows: Foam density: GB / T 6343—2009; Compression load (CLD 40%): ISO3386; Recovery time: GB / T 26392-2011; Tensile strength and elongation at break: ISO1798; Tear strength: GB / T 10808-2006; Drop ball rebound: GB / T 6670-2008; Compression set: GB / T 6669-2008.
[0051] The test result is: density 39.5 kg / m³ 3 The 40% compression load is 2.45 kPa, the recovery time is 6.6 s, the tensile strength is 62.53 kPa, the elongation at break is 178.73%, the tear strength is 291.27 N / m, and the 75% compression set is 7.32%.
[0052] Example 2 The raw material composition of a high-performance carbon dioxide-based polyurethane foam is as follows: 50 parts of polyether polyol A, 10 parts of polyether polyol B, 10 parts of polyether polyol C, 30 parts of carbon dioxide-based polyol, 1.4 parts of silicone oil surfactant, 3 parts of cell opener, 2.2 parts of chemical foaming agent, 0.18 parts of amine catalyst, 0.06 parts of tin catalyst, 3 parts of chain extender, 40.17 parts of toluene diisocyanate, and an isocyanate index of 90.
[0053] The types of raw materials are the same as in Example 1. The difference is that the carbon dioxide-based polyol is PPCD531 product from Dazhi Fine Chemical Co., Ltd., with 1,2-propanediol as the initiator, a molecular weight of 3000, a hydroxyl value of 37.6 mg KOH / g, propylene oxide and carbon dioxide as comonomers, with carbon dioxide content of 28% and propylene oxide PO content of 69%.
[0054] A method for preparing high-performance carbon dioxide-based polyurethane foam includes the following steps: The stoichiometric amounts of polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, and chain extender are mixed evenly to obtain the first component. At room temperature (23℃) and a rotation speed of 3000 rpm, stoichiometric amounts of toluene diisocyanate were added to the first component. After mixing thoroughly for 5 seconds, the mixture was injected into a mold at room temperature for 8 minutes and then cured for 40 minutes to obtain carbon dioxide-based polyurethane foam.
[0055] The obtained carbon dioxide-based polyurethane foam is a flexible foam with a density of 40.1 kg / m³. 3 The 40% compression load is 2.68 kPa, the recovery time is 7.1 s, the tensile strength is 74.71 kPa, the elongation at break is 161.31%, the tear strength is 331.71 N / m, and the 75% compression set is 5.37%.
[0056] Example 3 The raw material composition of a high-performance carbon dioxide-based polyurethane foam is as follows: 50 parts of polyether polyol A, 8 parts of polyether polyol B, 12 parts of polyether polyol C, 30 parts of carbon dioxide-based polyol, 2.0 parts of silicone oil surfactant, 3 parts of cell opener, 2.2 parts of chemical foaming agent, 0.18 parts of amine catalyst, 0.08 parts of tin catalyst, 4 parts of chain extender, 40.17 parts of toluene diisocyanate, and an isocyanate index of 90.
[0057] The types of raw materials are the same as in Example 1. The difference is that the carbon dioxide-based polyol is PPCD242 product from Dazhi Fine Chemical Co., Ltd., with 1,2-propanediol as the initiator, a molecular weight of 4000, a hydroxyl value of 28.4 mg KOH / g, propylene oxide and carbon dioxide as comonomers, with carbon dioxide content of 26% and propylene oxide PO content of 70%.
[0058] A method for preparing high-performance carbon dioxide-based polyurethane foam includes the following steps: The stoichiometric amounts of polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, and chain extender are mixed evenly to obtain the first component. At room temperature (23℃) and a rotation speed of 3000 rpm, stoichiometric amounts of toluene diisocyanate were added to the first component. After mixing thoroughly for 6 seconds, the mixture was injected into a mold at room temperature for 5 minutes and then cured for 60 minutes to obtain carbon dioxide-based polyurethane foam.
[0059] The obtained carbon dioxide-based polyurethane foam is a flexible foam with a density of 39.9 kg / m³. 3 The 40% compression load is 2.52 kPa, the recovery time is 3.9 s, the tensile strength is 75.98 kPa, the elongation at break is 191.32%, the tear strength is 338.65 N / m, and the 75% compression set is 5.43%.
[0060] Example 4 The raw material composition of a high-performance carbon dioxide-based polyurethane foam is as follows: 40 parts of polyether polyol A, 5 parts of polyether polyol B, 15 parts of polyether polyol C, 40 parts of carbon dioxide-based polyol, 1.4 parts of silicone oil surfactant, 4 parts of cell opener, 2.2 parts of chemical foaming agent, 0.18 parts of amine catalyst, 0.06 parts of tin catalyst, 3.5 parts of chain extender, and 40.17 parts of toluene diisocyanate with an isocyanate index of 90. The types of raw materials are the same as in Example 1, except that the carbon dioxide-based polyol used is the same product as in Example 2.
[0061] A method for preparing high-performance carbon dioxide-based polyurethane foam includes the following steps: The stoichiometric amounts of polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, and chain extender are mixed evenly to obtain the first component. At room temperature (23℃) and a rotation speed of 3000 rpm, stoichiometric amounts of toluene diisocyanate were added to the first component. After mixing thoroughly for 6 seconds, the mixture was injected into a mold at room temperature for 7 minutes and then cured for 60 minutes to obtain carbon dioxide-based polyurethane foam.
[0062] The obtained carbon dioxide-based polyurethane foam is a flexible foam with a density of 41.5 kg / m³. 3 The 40% compression load is 2.68 kPa, the recovery time is 6.6 s, the tensile strength is 58.4 kPa, the elongation at break is 155.66%, the tear strength is 288.55 N / m, and the 75% compression set is 5.86%.
[0063] Example 5 The raw material composition of a high-performance carbon dioxide-based polyurethane foam is as follows: 40 parts of polyether polyol A, 5 parts of polyether polyol B, 20 parts of polyether polyol C, 35 parts of carbon dioxide-based polyol, 2.0 parts of silicone oil surfactant, 4 parts of cell opener, 2.2 parts of chemical foaming agent, 0.18 parts of amine catalyst, 0.08 parts of tin catalyst, 3.5 parts of chain extender, and 37.15 parts of toluene diisocyanate with an isocyanate index of 90. The types of raw materials are the same as in Example 1, except that the carbon dioxide-based polyol used is the same product as in Example 3.
[0064] A method for preparing high-performance carbon dioxide-based polyurethane foam includes the following steps: The stoichiometric amounts of polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, and chain extender are mixed evenly to obtain the first component. At room temperature (23℃) and a rotation speed of 3000 rpm, stoichiometric amounts of toluene diisocyanate were added to the first component. After mixing thoroughly for 10 seconds, the mixture was injected into a mold at room temperature for 5 minutes and then cured for 60 minutes to obtain carbon dioxide-based polyurethane foam.
[0065] The obtained carbon dioxide-based polyurethane foam is a flexible foam with a density of 40.6 kg / m³. 3 The 40% compression load is 2.48 kPa, the recovery time is 7.8 s, the tensile strength is 61.86 kPa, the elongation at break is 185.55%, the tear strength is 295.18 N / m, and the 75% compression set is 8.96%.
[0066] Comparative Example 1 The types of raw materials are the same as in Example 1, except that carbon dioxide-based polyols are not used, and the cell opener is the Korean SKC Y-1900 product. The raw material composition of a polyurethane foam is as follows: 50 parts polyether polyol A, 40 parts polyether polyol B, 10 parts polyether polyol C, 1.4 parts silicone oil surfactant, 3 parts cell opener, 2.2 parts chemical foaming agent, 0.18 parts amine catalyst, 0.06 parts tin catalyst, 3 parts chain extender, and 40.17 parts toluene diisocyanate, with an isocyanate index of 90.
[0067] A method for preparing polyurethane foam includes the following steps: The stoichiometric amounts of polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, and chain extender are mixed evenly to obtain the first component. At room temperature (23℃) and a rotation speed of 3000 rpm, stoichiometric amounts of toluene diisocyanate were added to the first component. After mixing thoroughly for 5 seconds, the mixture was injected into a mold at room temperature for 8 minutes and then cured for 60 minutes to obtain carbon dioxide-based polyurethane foam.
[0068] The obtained carbon dioxide-based polyurethane foam is a flexible foam with a density of 39.3 kg / m³. 3 The 40% compression load is 2.39 kPa, the recovery time is 5.2 s, the tensile strength is 46.75 kPa, the elongation at break is 202.81%, the tear strength is 187.91 N / m, and the 75% compression set is 49.81%.
[0069] Comparative Example 2 The types of raw materials are the same as in Example 1, except that polyether polyol B is not used, and the cell opener is the Korean SKC Y-1900 product. The raw material composition of a polyurethane foam is as follows: 50 parts polyether polyol A, 10 parts polyether polyol C, 40 parts carbon dioxide-based polyol, 1.4 parts silicone oil surfactant, 3 parts cell opener, 2.2 parts chemical foaming agent, 0.18 parts amine catalyst, 0.06 parts tin catalyst, 3.5 parts chain extender, 40.17 parts toluene diisocyanate, with an isocyanate index of 90.
[0070] A method for preparing polyurethane foam includes the following steps: The stoichiometric amounts of polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, and chain extender are mixed evenly to obtain the first component. At room temperature (23℃) and a rotation speed of 3000 rpm, a stoichiometric amount of toluene diisocyanate was added to the first component. After mixing thoroughly for 6 seconds, the mixture was injected into a mold at room temperature for foaming for 8 minutes and then cured for 60 minutes. The resulting product exhibited abnormal foaming, was difficult to mold, and was not suitable for testing.
[0071] Comparative Example 3 The types of raw materials are the same as in Example 1, except that polyether polyol B is not used, and the chain extender is 1,4 Butanediol and carbon dioxide-based polyols are the same products used in Example 2, and the second cell opener is Huaian Bad BDM-4 type cell opener emulsion. The raw material composition of a carbon dioxide polyurethane foam is as follows: 50 parts polyether polyol A, 10 parts polyether polyol C, 40 parts carbon dioxide-based polyol, 1.4 parts silicone oil surfactant, 4 parts cell opener, 2.2 parts chemical foaming agent, 0.18 parts amine catalyst, 0.06 parts tin catalyst, 3 parts chain extender, and 40.17 parts toluene diisocyanate, with an isocyanate index of 90.
[0072] A method for preparing polyurethane foam includes the following steps: The stoichiometric amounts of polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, and chain extender are mixed evenly to obtain the first component. At room temperature (23℃) and a rotation speed of 3000 rpm, stoichiometric amounts of toluene diisocyanate were added to the first component. After mixing thoroughly for 5 seconds, the mixture was injected into a mold at room temperature for 8 minutes and then cured for 60 minutes to obtain carbon dioxide-based polyurethane foam.
[0073] The obtained carbon dioxide-based polyurethane foam is a flexible foam with a density of 38.5 kg / m³. 3 The 40% compression load is 2.40 kPa, the recovery time is 3.3 s, the tensile strength is 74.99 kPa, the elongation at break is 168.75%, the tear strength is 338.19 N / m, and the 75% compression set is 54.77%.
[0074] It can be seen that the polyurethane foam prepared using the raw material components of Comparative Examples 1-3 is either difficult to mold, or the resulting product has poor overall performance, or poor compression set (recovery), or recovers too quickly, or has defects in strength. However, the carbon dioxide-based polyurethane foam prepared using the technical solution of this invention in Examples 1-5 has good overall performance, and exhibits good performance in terms of density, resilience, compression set resistance, and strength. It can be used in cushions, seat cushions, mattresses, and other fields.
[0075] The above detailed description is a specific description of feasible embodiments of the present invention. These embodiments are not intended to limit the patent scope of the present invention. All equivalent implementations or modifications that do not depart from the present invention should be included in the patent scope of this case.
Claims
1. A high-performance carbon dioxide-based polyurethane foam, characterized in that, The polyurethane foam is a soft, slow-rebound foam with a density of 35-45 kg / m³. 3 40% compression load is 2.2-2.8 kPa, recovery time is 2-8 seconds, and 75% compression set is ≤10%.
2. A high-performance carbon dioxide-based polyurethane foam, characterized in that, The polyurethane foam is prepared from the following raw materials in parts by weight: 30-60 parts of polyether polyol A, 5-30 parts of polyether polyol B, 5-25 parts of polyether polyol C, 10-50 parts of carbon dioxide-based polyol, 1.0-2.0 parts of silicone oil surfactant, 1.0-5.0 parts of cell opener, 1.5-5.0 parts of chemical foaming agent, 0.15-0.30 parts of amine catalyst, 0.05-0.20 parts of tin catalyst, 1-5 parts of chain extender, and 38-42 parts of toluene diisocyanate, wherein the isocyanate index is 0.80-0.95; The polyether polyol A has a molecular weight of 500-800, a hydroxyl value of 200-300 mg KOH / g, a theoretical functionality of 3.0-3.5, an ethylene oxide (EO) content of 0%-5%, and a propylene oxide (PO) content of 80%-90%. The polyether polyol B has a molecular weight of 2500-3500, a hydroxyl value of 50-60 mg KOH / g, a theoretical functionality of 3.0, an EO content of 5%-13%, and a PO content of 85%-92%. The polyether polyol C has a molecular weight of 4000-5000, a hydroxyl value of 30-50 mg KOH / g, a theoretical functionality of 3.0, an EO content of 65%-80%, and a PO content of 20%-40%. The carbon dioxide-based polyol has a molecular weight of 2000-4000, a hydroxyl value of 28-56 mg KOH / g, a theoretical functionality of 2.0, a carbon dioxide content of 20-30%, and a PO content of 65%-75%.
3. The high-performance carbon dioxide-based polyurethane foam according to claim 2, characterized in that, The carbon dioxide-based polyol is a polycarbonate polyol containing carbonate bonds and ether bonds in its molecule. Its preparation raw materials include carbon dioxide, initiator, epoxide and catalyst. The epoxide is one or a combination of several of ethylene oxide, propylene oxide, 1,2-epoxybutane, epichlorohydrin and condensed glycerol.
4. The high-performance carbon dioxide-based polyurethane foam according to claim 3, characterized in that, The carbon dioxide-based polyol is a polypropylene carbonate polyol containing carbonate bonds and ether bonds within its molecule; the epoxide is propylene oxide; and the initiator is one or a combination of several of ethylene glycol, diethylene glycol, 1,3-propanetriol, 1,2-propanediol, and 1,4-butanediol.
5. The high-performance carbon dioxide-based polyurethane foam according to claim 4, characterized in that, The initiator is 1,2-propanediol, and the mass ratio of 1,2-propanediol, carbon dioxide and propylene oxide is 1:(5-16):(15-45).
6. The high-performance carbon dioxide-based polyurethane foam according to claim 2, characterized in that, The polyether polyol A is initiated by glycerol and pentaerythritol; the polyether polyols B and C are both copolymerized with glycerol as the initiator and ethylene oxide and propylene oxide as monomers.
7. The high-performance carbon dioxide-based polyurethane foam according to claim 2, characterized in that, The cell opener includes a first cell opener and a second cell opener, wherein the first cell opener is a polyether polyol-based soft slow-rebound foam cell opener and the second cell opener is a slow-rebound cell opener emulsion.
8. The high-performance carbon dioxide-based polyurethane foam according to claim 2, characterized in that, The chain extender is 1,4 A mixture of butanediol and PEG200, 1,4 The mass ratio of butanediol to PEG200 is 1:(0.2-0.5).
9. The high-performance carbon dioxide-based polyurethane foam according to claim 2, characterized in that, The silicone oil surfactant is soft foam slow rebound silicone oil B8002 or / and soft foam slow rebound silicone oil L-838; or / and the amine catalyst is triethylenediamine; or / and the tin catalyst is stannous neodecanoate; or / and the chemical foaming agent is water.
10. A method for preparing high-performance carbon dioxide-based polyurethane foam as described in any one of claims 1 to 9, characterized in that, Includes the following steps: The stoichiometric amounts of polyether polyol A, polyether polyol B, polyether polyol C, carbon dioxide-based polyol, silicone oil surfactant, cell opener, physical foaming agent, amine catalyst, tin catalyst, and chain extender are mixed evenly to obtain the first component. At room temperature and a rotation speed of 2000-4000 rpm, stoichiometric amounts of toluene diisocyanate are added to the first component. After mixing and reacting for 3-8 seconds, the mixture is injected into a box mold at room temperature or a closed mold at 40-80℃ for foaming reaction for 2-10 minutes. After curing, carbon dioxide-based polyurethane foam is obtained.