Polyurethane plate taking regenerated polyether polyol as raw material and preparation method of polyurethane plate

Abstract

The invention relates to a polyurethane plate produced by taking regenerated polyether polyol as a raw material and a preparation method thereof, and mainly solves the problems of high cost and no environmental protection caused by using petroleum-based polyether in polyurethane foam in the prior art. The polyurethane board using the regenerated polyether polyol as the raw material is composed of a component A and a component B, the weight ratio of the component A to the component B is 1: (1.3-1.6), the component A comprises, by weight, 10-30 parts of polyether polyol I, 20-40 parts of polyether polyol II, 5-10 parts of polyether polyol III, 10-30 parts of regenerated polyether polyol and 5-15 parts of low-aldehyde polyether polyol, and the component B comprises, by weight, 10-30 parts of polyether polyol I, 20-40 parts of polyether polyol II, 5-10 parts of polyether polyol III, 10-30 parts of regenerated polyether polyol and 5-15 parts of low-aldehyde polyether polyol. The foaming agent comprises the following components in parts by weight: 5-10 parts of dihydric alcohol, 0.1-0.5 part of a reaction type catalyst, 0.1-1.0 part of a foam stabilizer I, 0.1-1.0 part of a foam stabilizer II, 0.5-1.5 parts of an opening agent and 3-6 parts of water. The component B is a mixture of two kinds of polymerized MDI, and the weight percentage ratio of the two kinds of polymerized MDI is 1: (0.1-1.0), the problem is well solved, and the composition can be used for industrial application of automobile roofs.

Description

Technical Field

[0001] The present invention relates to the field of polyurethane material preparation, in particular to a polyurethane plate using recycled polyether polyol as a raw material and a preparation method thereof. Background Art

[0002] Polyurethane foam is widely used in the automotive, construction, and furniture industries due to its excellent thermal insulation, sound insulation, and shock absorption properties. Traditional polyurethane foam is primarily produced by reacting polyether polyols (polyether polyols) with isocyanates, with polyether polyols primarily derived from petroleum resources. With the increasing depletion of petroleum resources and growing environmental awareness, the development of low-cost, environmentally friendly polyurethane foam has become a hot topic in industry research.

[0003] At present, the preparation of polyurethane foam materials mainly adopts petroleum-based polyether polyols as raw materials. Such raw materials are not only costly but also environmentally unfriendly.

[0004] In order to solve this problem, researchers began to explore the technical route of using bio-based polyethers and recycled polyols to replace part of the petroleum-based polyethers. However, the existing technology has the following problems: First, the proportion of recycled polyether polyols is limited, making it difficult to significantly reduce material costs; second, recycled polyether polyols usually have odor problems, which limits their application in high-end products; third, the polyurethane foam materials in the existing technology often find it difficult to strike a balance between cost and performance while meeting environmental protection requirements. Therefore, it is of great practical significance to develop a low-cost, green and environmentally friendly polyurethane foam material that uses a high proportion of recycled polyether polyols while maintaining good physical and mechanical properties.

[0005] Chinese patent CN114456344A discloses a low-carbon and environmentally friendly all-bio-based semi-rigid polyurethane foam formula. This formula uses bio-based polyether, recycled polyol and bio-based isocyanate as raw materials to produce semi-rigid polyurethane foam. The polyurethane material prepared by this invention has a density of 40kg / m3, a compressive strength of 150kPa, a tensile strength of 180kPa and an elongation of about 15%. The overall density is too high and the general elongation cannot meet the requirements of the increasingly complex molding mold cavity.

[0006] Chinese patent CN117659502A discloses a method for preparing recycled polyether polyols from waste polyurethane rigid foam and its application. The polyurethane foam material prepared by this invention is mainly used in the field of rigid foam insulation and has excellent compressive strength and thermal insulation properties. Summary of the Invention

[0007] One of the technical problems to be solved by the present invention is that the polyurethane sheet material used for automobile roofs in the prior art mainly uses petroleum-based polyether polyols, which are high in cost and not environmentally friendly. In order to solve the problem of high cost and environmental pollution of petroleum-based polyethers used in polyurethane foam in the prior art and to achieve low-cost and environmentally friendly preparation of polyurethane foam materials, the present invention provides a polyurethane sheet using recycled polyether polyols as raw materials.

[0008] The second technical problem to be solved by the present invention is to provide a method for preparing a polyurethane sheet using recycled polyether polyol as a raw material, which corresponds to the first technical problem to be solved.

[0009] To solve one of the above technical problems, the present invention adopts the following technical solution: comprising component A and component B, wherein the weight percentage of component A to component B is 1:1.3-1.6, wherein component A comprises, by weight, 10-30 parts of polyether polyol I, 20-40 parts of polyether polyol II, 5-10 parts of polyether polyol III, 10-30 parts of recycled polyether polyol, 5-15 parts of low-aldehyde polyether polyol, 5-10 parts of diol, 0.1-0.5 parts of reaction catalyst, 0.1-1.0 parts of foam stabilizer I, 0.1-1.0 parts of foam stabilizer II, 0.5-1.5 parts of cell opener, and 3-6 parts of water; component B is a mixture of two polymeric MDIs, and the weight percentage ratio of the two is 1:0.1-1.0;

[0010] The polyether polyol I is a polyether polyol formed by polymerizing ethylene oxide and propylene oxide with at least one of glycerol, trimethylolpropane or sorbitol as an initiator, and is terminated with ethylene oxide, has a functionality of 3, and a molecular weight of 3000-8000; the polyether polyol II is a polyether polyol formed by block polymerization of propylene oxide with at least one of diethylene glycol, glycerol, pentaerythritol, ethylenediamine, sucrose or sorbitol as an initiator, and has a functionality of 3 and an average molecular weight of 300-1000; the polyether polyol III is a polyether polyol formed by block polymerization of propylene oxide with at least one of propylene glycol, trimethylolpropane or glycerol as an initiator, and is terminated with propylene oxide or ethylene oxide. At least one polymerized polyether polyol has a functionality of 2 and an average molecular weight of 400-3000; the recycled polyether polyether is prepared by mixing polyurethane semi-rigid foam scraps in a certain weight ratio and crushing them using a foam crusher to obtain polyurethane semi-rigid foam particles; the polyurethane semi-rigid foam particles are mixed and dissolved with an alcoholysis agent and a catalyst, subjected to heat preservation reaction, and subjected to reduced pressure distillation to remove small molecules. After cooling and filtration, the polyether odor is improved by short-path evaporation to obtain the recycled polyether polyol; the low-aldehyde polyether polyol is obtained by distilling CHE-828 polyether mixed with hydrazine hydrate, TDI, and water to obtain polyurea polyol, and then mixing it with CHE-828 again;

[0011] The diol has a functionality of 2, a molecular weight of 50 to 150, and a hydroxyl value of 750 to 2500 mgKOH / g; the reaction catalyst is a tertiary amine catalyst containing hydroxyl groups; the foam stabilizer is a polysiloxane-olefin oxide block copolymer; and the pore opener is a polyolefin oxide-polysiloxane copolymer.

[0012] In the above scheme, preferably, the polyether polyol I is selected from at least one of CHE-2801, CHE-330N, BD3-3000A or NJ-360N; the polyether polyol II is selected from at least one of CHE-307, CHE-304, CHE-303 or TMN-450; and the polyether polyol III is selected from at least one of CHE-204, CHE-210, NJ-230 or CHE-220.

[0013] In the above scheme, preferably, the diol is selected from at least one of ethylene glycol, diethylene glycol, 1,4-butanediol or dipropylene glycol.

[0014] In the above scheme, preferably, the foam stabilizer I is selected from at least one of B8870, B8409 or B8228; and the foam stabilizer II is selected from at least one of AK-8805, B8444 or L-6915.

[0015] In the above solution, preferably, the polyoxyalkylene-polysiloxane copolymer is ORTEGOL 501.

[0016] In the above scheme, preferably, the reaction catalyst is selected from at least one of ECOADD 1055LE, PC17, DMEA or PC37.

[0017] In the above scheme, preferably, the polymeric MDI mixture is selected from at least two of MIPS, MDI50, S3051, M20S, PM200 or 44V20L.

[0018] To solve the second technical problem mentioned above, the present invention adopts the following technical solution: a method for preparing a polyurethane sheet using recycled polyether polyol as raw material, comprising the following steps:

[0019] (1) Preparation of component A: In container A, add 10-30 parts of polyether polyol I, 20-40 parts of polyether polyol II, 5-10 parts of polyether polyol III, 10-30 parts of regenerated polyether polyol, 5-15 parts of low-aldehyde polyether polyol, 5-10 parts of diol, 0.1-0.5 parts of reaction catalyst, 0.1-1.0 parts of foam stabilizer I, 0.1-1.0 parts of foam stabilizer II, 0.5-1.5 parts of cell opener, and 3-6 parts of water in order by weight, and stir uniformly at a temperature of 20-23° C. to obtain component A;

[0020] (2) Preparation of component B: Add two polymeric MDIs in a ratio of 1:0.5 to 1.0 by weight to container B, and stir evenly at 20 to 23° C. to obtain component B;

[0021] (3) Component A and component B are mixed in a weight percentage ratio of 1:1.3 to 1.6 parts, and the ambient temperature is controlled at 20 to 23°C. The mixture is quickly mixed and stirred, and immediately poured into a pre-prepared foaming box after stirring evenly. After free foaming is completed, the polyurethane sheet is obtained after waiting for aging to complete.

[0022] The polyurethane sheet material using recycled polyether polyol as raw material provided by the present invention effectively reduces the production cost of polyurethane foam materials by using recycled polyether polyol to replace part of traditional petroleum-based polyether polyol, and at the same time realizes the recycling of resources, which is in line with the development concept of green environmental protection. At the same time, by using a reasonable ratio of polyether polyols with different molecular weights and recycled polyether polyols, and matching suitable silicone oil and catalyst ratios, it is ensured that the physical properties of the product are not affected. At the same time, the present invention further reduces the aldehyde content in the product by adding low-aldehyde polyether polyol, improves the environmental performance of the product, and reduces harm to the human body. The polyurethane foam material of the present invention can be applied to industrial fields such as automobile roofs, has good market application prospects, and provides a new technical path for the green and environmental development of polyurethane foam materials. Good technical results have been achieved. DETAILED DESCRIPTION

[0023] The present invention is further described below by way of examples, but is not limited thereto.

[0024] Table 1 List of raw materials

[0025]

[0026]

[0027] In Table 1, the preparation method of the regenerated polyether polyol is obtained by referring to the preparation method disclosed in Chinese patent CN 118930965A, wherein the hydroxyl value of the regenerated polyether polyol is between 450 and 650 mgKOH / g, and the acid value is between 0.1 and 1.5 mgKOH / g.

[0028] [Example 1]

[0029] A method for preparing a polyurethane sheet using recycled polyether polyol as raw material comprises the following steps:

[0030] (1) Preparation of component A:

[0031] In container A, add CHE-330N, CHE-304, CHE-210, DEG, CFS-6000, recycled polyether polyol, B-8228, AK-8805, ECOADD 1055LE, cell opener ORTEGOL 501 and water in sequence, and stir evenly at 20-23°C to obtain component A;

[0032] (2) Preparation of component B:

[0033] Add M20s and S3051 to container B in sequence, and stir evenly at 20-23°C to obtain component B;

[0034] After quickly mixing and stirring component A and component B evenly, pour them into the foaming box prepared in advance, and allow them to rise freely. After waiting for aging, the polyurethane sheet is obtained. Its performance index parameters are shown in Table 3.

[0035] [Examples 2 to 5]

[0036] Examples 2 to 5 were carried out according to the steps in Example 1, except that the reaction raw materials and raw material ratios in the foaming formula were different, as shown in Table 2. The performance index data of the obtained polyurethane sheets are shown in Table 3.

[0037] Table 2 Weight parts of each component in the polyurethane sheet formula of Examples 1 to 5

[0038]

[0039]

[0040]

[0041] Comparative Example 1

[0042] A method for preparing a polyurethane sheet material comprises the following steps:

[0043] (1) Prepare the following raw materials by weight:

[0044] Component A: 100 parts specifically 45 parts CHE-330N, 40 parts CHE-304, 8 parts DEG, 0.3 parts PC37, 0.6 parts B-8409, 1.5 parts pore opener ORTEGOL 501, 4.6 parts water

[0045] Component B: 140 parts, specifically 91 parts M20s and 49 parts MIPS

[0046] (2) Preparation of component A:

[0047] According to the weight parts in step (1), CHE-330N, CHE-304, diethylene glycol, PC37, B-8409, ORTEGOL 501, and water were added to container A in sequence, and stirred at 20-23° C. to obtain component A;

[0048] (3) Preparation of component B:

[0049] Add M20s and MIPS to container B according to the weight parts in step (1), and stir evenly at 20-23°C to obtain component B;

[0050] After quickly mixing and stirring component A and component B evenly, quickly pour them into a pre-prepared foaming box. After free rising is completed, wait for aging to complete to obtain the polyurethane sheet material. Its performance indicators are shown in Table 3.

[0051] Comparative Example 2

[0052] A method for preparing a polyurethane sheet material comprises the following steps:

[0053] (1) Prepare the following raw materials by weight:

[0054] Component A: 100 parts specifically 10 parts CHE-330N, 15 parts CHE-304, 40 parts recycled polyether polyol, 10 parts CHE-210, 10 parts CFS-6000, 8 parts DEG, 0.4 parts ECOADD 1055LE, 0.2 parts 8870, 0.2 parts 8805, 1.4 parts cell opener ORTEGOL 501, 4.8 parts water

[0055] Component B: 150 parts, specifically 97.5 parts M20s and 52.5 parts S3051

[0056] (2) Preparation of component A:

[0057] According to the weight parts in step (1), CHE-330N, CHE-304, recycled polyether polyol, CHE-210, CFS-6000, DEG, ECOADD 1055LE, 8870, 8805, ORTEGOL 501, water,

[0058] , stir evenly at 20-23°C to obtain component A;

[0059] (3) Preparation of component B:

[0060] Add M20s and S3051 to container B according to the weight parts in step (1), and stir evenly at 20-23°C to obtain component B;

[0061] After quickly mixing and stirring component A and component B evenly, quickly pour them into a pre-prepared foaming box. After free rising is completed, wait for aging to complete to obtain the polyurethane sheet material. Its performance indicators are shown in Table 3.

[0062] Table 3 Performance test data of polyurethane sheets of Examples 1 to 5 and Comparative Examples 1 to 2

[0063]

[0064] The data in Table 3 show that, compared with Comparative Example 1, Examples 1-5, when adding a high percentage of recycled polyether polyol, exhibit an increase in tensile and compressive strength in the overall foam performance. However, the introduction of long-chain polyether moderately reduces crosslink density, thereby improving flexibility. Furthermore, a more appropriate proportion of isocyanate is used to further mitigate the decrease in toughness caused by the increased strength, and a suitable silicone oil catalyst ratio is used. Ultimately, the foam elongation at break remains >24%. Furthermore, the introduction of an appropriate amount of short-steamed recycled polyether polyol does not significantly alter the foam odor, essentially consistent with commercially available products. The resulting polyurethane sheets exhibit excellent performance, are lower cost, and are more environmentally friendly. Compared with Comparative Example 2, Examples 1-5, when adding an excessive amount of recycled polyether, significantly improve the foam's rigidity, but at the same time sacrifice toughness, potentially leading to the risk of tearing and fracture during the subsequent sheet application and compounding process. Furthermore, an excessive amount of recycled polyether polyol amplifies the residual odor produced during the polyether recovery process, resulting in a stronger product odor.

[0065] Therefore, the polyurethane sheet provided by the present invention, which uses recycled polyether polyol as a raw material, has the advantage of maintaining the overall performance unchanged while reducing resource waste and protecting the environment. It can also reduce the generation of semi-rigid foam scraps of polyurethane automobile roofs and can be recycled in the production of semi-rigid foam automobile roofs, achieving good technical effects and being applicable to practical applications of automobile roofs.

Claims

1. A polyurethane sheet made from recycled polyether polyol, characterized by: The polyurethane sheet product is composed of component A and component B, with component A and component B being in a weight percentage ratio of 1:1.3-1.6, wherein component A comprises, by weight, 10-30 parts of polyether polyol I, 20-40 parts of polyether polyol II, 5-10 parts of polyether polyol III, 10-30 parts of recycled polyether polyol, 5-15 parts of low-aldehyde polyether polyol, 5-10 parts of diol, 0.1-0.5 parts of reaction catalyst, 0.1-1.0 parts of foam stabilizer I, 0.1-1.0 parts of foam stabilizer II, 0.5-1.5 parts of cell opener, and 3-6 parts of water; component B is a mixture of two polymeric MDIs, with the weight percentage ratio of the two being 1:0.1-1.0; The polyether polyol I is a polyether polyol formed by polymerizing ethylene oxide and propylene oxide with at least one of glycerol, trimethylolpropane or sorbitol as an initiator, and is terminated with ethylene oxide, has a functionality of 3, and a molecular weight of 3000-8000; the polyether polyol II is a polyether polyol formed by block polymerization of propylene oxide with at least one of diethylene glycol, glycerol, pentaerythritol, ethylenediamine, sucrose or sorbitol as an initiator, and has a functionality of 3 and an average molecular weight of 300-1000; the polyether polyol III is a polyether polyol formed by block polymerization of propylene oxide with at least one of propylene glycol, trimethylolpropane or glycerol as an initiator, and is terminated with propylene oxide or ethylene oxide. At least one polymerized polyether polyol has a functionality of 2 and an average molecular weight of 400-3000; the recycled polyether polyether is prepared by mixing polyurethane semi-rigid foam scraps in a certain weight ratio and crushing them using a foam crusher to obtain polyurethane semi-rigid foam particles; the polyurethane semi-rigid foam particles are mixed and dissolved with an alcoholysis agent and a catalyst, subjected to heat preservation reaction, and subjected to reduced pressure distillation to remove small molecules. After cooling and filtration, the polyether odor is improved by short-path evaporation to obtain the recycled polyether polyol; the low-aldehyde polyether polyol is obtained by distilling CHE-828 polyether mixed with hydrazine hydrate, TDI, and water to obtain polyurea polyol, and then mixing it with CHE-828 again; The diol has a functionality of 2 and a molecular weight of 50 to 150; the reaction catalyst is a tertiary amine catalyst containing a hydroxyl group; the foam stabilizer I and the foam stabilizer II are polysiloxane-olefin oxide block copolymers; and the cell opener is a polyolefin oxide-polysiloxane copolymer.

2. The polyurethane sheet made of recycled polyether polyol according to claim 1, characterized in that: The polyether polyol I is selected from at least one of CHE-2801, CHE-330N, BD3-3000A or NJ-360N; the polyether polyol II is selected from at least one of CHE-307, CHE-304, CHE-303 or TMN-450; the polyether polyol III is selected from at least one of CHE-204, CHE-210, NJ-230 or CHE-220.

3. The polyurethane sheet made of recycled polyether polyol according to claim 1, characterized in that: The diol is selected from at least one of ethylene glycol, diethylene glycol, 1,4-butanediol or dipropylene glycol.

4. The polyurethane sheet made of recycled polyether polyol according to claim 1, characterized in that: The foam stabilizer I is selected from at least one of B8870, B8409 or B8228; the foam stabilizer II is selected from at least one of AK-8805, B8444 or L-6915.

5. The polyurethane sheet made of recycled polyether polyol according to claim 1, characterized in that: The polyoxyalkylene-polysiloxane copolymer is ORTEGOL 501.

6. The polyurethane sheet made of recycled polyether polyol according to claim 1, characterized in that: The reaction catalyst is selected from at least one of ECOADD 1055LE, PC17, DMEA or PC37.

7. The polyurethane sheet made of recycled polyether polyol according to claim 1, characterized in that: The polymeric MDI mixture is selected from at least two of MIPS, MDI50, S3051, M20S, PM200 or 44V20L.

8. A method for preparing a polyurethane sheet using recycled polyether polyol as a raw material according to claim 1, comprising the following steps: (1) Preparation of component A: In container A, add 10-30 parts of polyether polyol I, 20-40 parts of polyether polyol II, 5-10 parts of polyether polyol III, 10-30 parts of regenerated polyether polyol, 5-15 parts of low-aldehyde polyether polyol, 5-10 parts of diol, 0.1-0.5 parts of reaction catalyst, 0.1-1.0 parts of foam stabilizer I, 0.1-1.0 parts of foam stabilizer II, 0.5-1.5 parts of cell opener, and 3-6 parts of water in order by weight, and stir uniformly at a temperature of 20-23° C. to obtain component A; (2) Preparation of component B: Add two polymeric MDIs in a ratio of 1:0.5 to 1.0 by weight to container B, and stir evenly at 20 to 23° C. to obtain component B; (3) Component A and component B are mixed in a weight percentage ratio of 1:1.3 to 1.6 parts, and the ambient temperature is controlled at 20 to 23°C. The mixture is quickly mixed and stirred, and immediately poured into a pre-prepared foaming box after stirring evenly. After free foaming is completed, the polyurethane sheet is obtained after waiting for aging to complete.

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