All-water open-cell high-temperature-resistant polyurethane foam product for food fermentation tank and preparation method of all-water open-cell high-temperature-resistant polyurethane foam product

Abstract

The invention discloses a full-water open-cell type high-temperature-resistant polyurethane foam product for a food fermentation tank and a preparation method of the full-water open-cell type high-temperature-resistant polyurethane foam product, and belongs to the technical field of polyurethane foam materials. The polyurethane foam product is prepared from a component A and a component B, wherein the mass ratio of the component A to the component B is 100: (100-105); the component A consists of the following components in parts by weight: 100 parts of melamine polyether polyol, 10-25 parts of a halogen-free flame retardant, 1-2 parts of a foam stabilizer, 0.5-1.5 parts of a pore opening agent, 0.5-2 parts of a catalyst composition and 3-4 parts of deionized water; and the component B is polymethyl polyphenyl polyisocyanate PM-400 of which the functionality is greater than 2.2. The production cost is low, the production efficiency is high, construction is convenient, and the obtained foam product has good mechanical property and flame retardant property, is excellent in heat preservation effect and can meet the use requirements of high-temperature scenes.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane foam materials, and more specifically, to a water-filled open-cell high-temperature resistant polyurethane foam product for food fermentation tanks and a preparation method thereof. Background Art

[0002] Asbestos and rock wool have good high-temperature resistance (the temperature resistance range of asbestos is above 1200 °C, and the temperature resistance range of rock wool is 400 - 700 °C). However, since both of them contain a large amount of harmful substances such as asbestos and alumina dust in their components, long-term contact is likely to cause skin allergies, throat discomfort, eye diseases, bronchitis, lung cancer and other diseases, and they have been successively prohibited in many industries. Due to their relatively high thermal conductivity (the thermal conductivity of rubber and plastic insulation materials is 0.034 - 0.041 W / (m·K), and the thermal conductivity of aluminum silicate is 0.05 W / (m·K)), the heat insulation performance of rubber and plastic insulation materials and aluminum silicate is average, and they are also subject to certain restrictions or do not meet the requirements of some products.

[0003] Polyurethane (PU) is a polymer material with a variety of excellent properties, such as being lightweight, sound-insulating, shock-absorbing, flame-retardant, oil-resistant, and having good chemical properties. Especially, its performance is outstanding in low-temperature environments (this is due to the interaction between the soft segments and hard segments in the polyurethane molecular structure, which makes it have good flexibility and elasticity and can still maintain good physical properties at low temperatures). However, compared with its low-temperature performance, the high-temperature resistance of polyurethane is indeed average (its temperature resistance range is usually -60 to 80 °C). In high-temperature environments (when the temperature exceeds 100 °C), the polyurethane foam will undergo deformations such as expansion or contraction, which is mainly related to its thermal stability and heat-resistant oxidation performance.

[0004] Therefore, if a polyurethane foam product with excellent heat insulation effect and environmental protection and safety can be developed, it will have broad application prospects and meet the use requirements of high-temperature scenarios. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above-mentioned deficiencies of the prior art, and provide a water-filled open-cell high-temperature resistant polyurethane foam product for food fermentation tanks and a preparation method thereof, which have low production costs, high production efficiency, convenient construction, the obtained foam product has good mechanical properties and flame retardancy, and excellent heat insulation effect, and can meet the use requirements of high-temperature scenarios.

[0006] To achieve the above purpose, the present invention adopts the following technical solutions:

[0007] A fully water-open cell type high-temperature resistant polyurethane foam product for a food fermentation tank, which is made from component A and component B, and the mass ratio of component A to component B is 100:100 - 105; Component A consists of the following components by weight: 100 parts of melamine polyether polyol, 10 - 25 parts of halogen-free flame retardant, 1 - 2 parts of foam stabilizer, 0.5 - 1.5 parts of cell opener, 0.5 - 2 parts of catalyst composition, 3 - 4 parts of deionized water; Component B is polymethylpolyphenyl polyisocyanate PM-400 with a functionality greater than 2.2.

[0008] The present invention is further configured such that the halogen-free flame retardant is flame retardant TEP.

[0009] The present invention is further configured such that the foam stabilizer is silicone oil Niax Y-16429.

[0010] The present invention is further configured such that the cell opener is ORTEGOL 501.

[0011] The present invention is further configured such that the catalyst composition is a composition of reactive catalyst PC-37 and reactive catalyst PC-31.

[0012] The present invention is further configured such that the melamine polyether polyol is made by ring-opening polymerization of melamine formaldehyde resin and propylene oxide under catalyst conditions, with a functionality of 4 and a hydroxyl value of 300 mgKOH / g.

[0013] The present invention is further configured such that it is made from component A and component B, and the mass ratio of component A to component B is 100:100; Component A consists of the following components by weight: 100 parts of melamine polyether polyol, 20 parts of halogen-free flame retardant TEP, 1.8 parts of silicone oil Niax Y-16429, 0.8 part of ORTEGOL 501, 0.8 part of reactive catalyst PC-37, 0.2 part of reactive catalyst PC-31, 3.5 parts of deionized water; Component B is polymethylpolyphenyl polyisocyanate PM-400 with a functionality greater than 2.2.

[0014] A preparation method of a fully water-open cell type high-temperature resistant polyurethane foam product for a food fermentation tank, wherein each component of component A is put into a container and stirred evenly to obtain component A; then component A and component B are mixed according to the mass ratio and foamed by a high-pressure foaming machine to obtain the fully water-open cell type high-temperature resistant polyurethane foam product for a food fermentation tank.

[0015] In summary, the present invention has the following beneficial effects:

[0016] 1. Using polyether and highly functional isocyanate in a certain proportion as raw materials, with reactive catalysts PC-37 and PC-31 as catalysts, and adding foam stabilizer silicone oil Niax Y-16429 and cell opener ORTEGOL 501, foam construction is carried out through a high-pressure foaming machine to obtain a rigid open-cell polyurethane foam thermal insulation material. The construction is flexible and convenient, very suitable for construction operations in the inner cavities of various complex and irregular tanks. The construction is simple, the production efficiency is high, and the cost is low.

[0017] 2. The obtained open-cell polyurethane foam material is light in weight, its mechanical properties meet the requirements, it has good high-temperature dimensional stability and excellent thermal stability, and has excellent flame retardant properties, which can meet the requirements of Class B2 in the combustion performance grade and classification basis of flat building materials and products in the National Standard GB8624-2021 "Classification of Combustion Performance of Building Materials and Products". Specific Embodiments

[0018] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0019] A fully water-based open-cell high-temperature resistant polyurethane foam product for food fermentation tanks, consisting of component A and component B; Component A is composed of the following components (by weight): 100 parts of melamine polyether polyol, 10-25 parts of halogen-free flame retardant, 1-2 parts of foam stabilizer, 0.5-1.5 parts of cell opener, 0.5-2 parts of catalyst composition, 3-4 parts of deionized water; Component B is polymethyl polyphenyl polyisocyanate PM-400 with a functionality greater than 2.2 (manufactured by Yantai Wanhua Polyurethane Co., Ltd.).

[0020] In Component A, the melamine polyether polyol is prepared by ring-opening polymerization of melamine formaldehyde resin and propylene oxide under catalyst conditions. Its functionality is 4 and the hydroxyl value is 300 mgKOH / g. The specific preparation method refers to the method described in the patent "A Preparation Method of Melamine Resin-based Flame Retardant Polyether Polyol" (publication number: CN110894289A). The flame retardant is a halogen-free flame retardant TEP, whose Chinese name is triethyl phosphate. It does not contain chlorine ions and will not cause intergranular corrosion on the surface of stainless steel. The foam stabilizer is silicone oil Niax Y-16429, and the manufacturer is Momentive Performance Materials Inc. The cell opener is ORTEGOL 501, and the manufacturer is Evonik Industries AG (EVONIK). The catalyst composition is a combination of Catalyst A and Catalyst B. Catalyst A is a reactive catalyst PC-37 (Chinese name: dimethylaminoethoxyethanol, English name: Polycat37), and Catalyst B is a reactive catalyst PC-31 (English name: Polycat 31). The blowing agent is deionized water, and the ozone depletion potential (ODP) of the generated gas carbon dioxide during the foaming process is zero. It is non-toxic, safe, and more environmentally friendly.

[0021] The following table shows the parameter comparison between Component B and ordinary isocyanate in the present invention:

[0022] Project Common Isocyanate High-functional Isocyanate PM-400 Viscosity (25℃) / mPa·s 150～250 350～400 Isocyanate Group Content (-NCO) / % 30.5～32.0 30.5～32.0 <![CDATA[Density (25 °C) / g / cm 3 )]]> 1.220～1.250 1.220～1.250 Functionality 2 Greater than 2.2

[0023] Put the components of Component A into a container according to the proportion and stir evenly. Then mix Component A and Component B in a weight ratio of A:B = 100:100 - 105. The obtained mixture is foamed by a high-pressure device (high-pressure foaming machine) (the foaming temperature is 20 - 25 °C), and a fully water-open-cell high-temperature resistant polyurethane foam product for food fermentation tanks can be made.

[0024] The preferred embodiments are as follows:

[0025] Example 1

[0026] A fully water-open-cell high-temperature resistant polyurethane foam product for food fermentation tanks is composed of Component A and Component B. Component A consists of the following components (by weight): 100 parts of melamine polyether polyol, 20 parts of halogen-free flame retardant TEP, 1.8 parts of foam stabilizer (silicone oil Niax Y-16429), 0.8 parts of cell opener (ORTEGOL 501), 0.8 parts of Catalyst A (reactive catalyst PC-37), 0.2 parts of Catalyst B (reactive catalyst PC-31), and 3.5 parts of deionized water. Component B is a polymethylpolyphenyl polyisocyanate PM-400 with functionality greater than 2.2. Component B is a high-functionality polymethylpolyphenyl polyisocyanate PM-400.

[0027] Prepare Component A (i.e., put the above raw materials in parts by weight into a container and stir evenly to obtain a polyether blend for open-cell high-temperature resistant polyurethane); then mix Components A and B in a weight ratio of A:B = 100:100, and foam through a high-pressure foaming machine at 25°C to obtain the all-water open-cell high-temperature resistant polyurethane foam product for food fermentation tanks.

[0028] Examples 2 - 4

[0029] Prepare polyurethane foam products according to the addition amounts of the foam stabilizer and the cell opener shown in the following table and by the method of Example 1 (i.e., in Examples 2 - 4, except for the different addition amounts of the foam stabilizer and the cell opener, the rest are the same as in Example 1).

[0030] Component Example 2 Example 3 Example 4 Foam Stabilizer 1.5 parts by mass 2 parts by mass 1 part by mass Cell-Opening Agent 1 part by mass 0.5 part by mass 1.5 parts by mass

[0031] Conduct performance tests on the polyurethane foam materials prepared in Examples 1 - 4 respectively, and the results are shown in the following table:

[0032] Number Example 1 Example 2 Example 3 Example 4 Cell-Opening Rate (%) 78 92 62 95 Thermal Conductivity (w / m.k) 0.028 0.030 0.026 / Dimensional Stability at 100℃ / 48 hours Intact Intact Shrinkage Foam Collapse Cell Size Fine Cells Fine Cells Fine Foam Coarse Foam

[0033] Draw the following conclusions based on the data analysis in the above table:

[0034] 1. As the usage amount of the cell opener D501 increases, the cell opening rate of the foam product also increases significantly.

[0035] 2. As the cell opening rate increases, the thermal conductivity of the foam also increases significantly, and the heat insulation effect becomes worse; too high a cell opening rate will cause the foam cells to be too thick and even collapse.

[0036] The products obtained in Examples 1 and 2 can meet all performance requirements at the same time. Among them, the compressive strengths of the polyurethane foam materials obtained in Examples 1 and 2 are 225 kPa and 202 kPa respectively, and the flame retardant performance also reaches Class B2.

[0037] Comparative Example 1

[0038] Prepare polyurethane foam by the method of Example 1, but without adding the foam stabilizer silicone oil Niax Y - 16429.

[0039] Comparative Example 2

[0040] Prepare polyurethane foam by the method of Example 1, but without adding the cell opener ORTEGOL 501.

[0041] Comparative Example 3

[0042] Prepare polyurethane foam by the method of Example 1, but replace the foam stabilizer silicone oil Niax Y - 16429 with the same mass of the foam stabilizer B8715.

[0043] Comparative Example 4

[0044] Prepare the polyurethane foam according to the method of Example 1, but replace the blowing agent ORTEGOL 501 with the blowing agent AK-9901 in equal mass.

[0045] Experiments found that the polyurethane material in Comparative Example 1 had serious shrinkage phenomenon, and in Comparative Example 2, local hollow and foam collapse phenomena occurred inside the foam during the foaming process, and products meeting the performance requirements could not be obtained. The polyurethane foam materials prepared in Example 1, Comparative Example 3, and Comparative Example 4 were respectively subjected to performance tests, and it was found that the compressive strengths of the polyurethane foam materials in Comparative Example 3 and Comparative Example 4 were respectively reduced by 61 kPa and 84 kPa compared with that of the polyurethane foam material in Example 1. The dimensional shrinkage rate (135 °C, 48 hours) of the polyurethane foam material in Example 1 was only 0.8%, and it had good high-temperature dimensional stability. While the dimensional shrinkage rates (135 °C, 48 hours) of the polyurethane foam materials in Comparative Example 3 and Comparative Example 4 were 6.4% and 5.92% respectively, and their high-temperature dimensional stability was poor. It can be seen that only by adding the foam stabilizer silicone oil Niax Y-16429 and the blowing agent ORTEGOL 501 simultaneously can the compressive strength and high-temperature dimensional stability of the polyurethane foam material be significantly improved, and polyurethane foam products with excellent heat insulation effect can be obtained.

[0046] Comparative Example 5

[0047] Prepare the polyurethane foam according to the method of Example 1, but without adding the reactive catalyst PC-31.

[0048] Comparative Example 6

[0049] Prepare the polyurethane foam according to the method of Example 1, but without adding the reactive catalyst PC-37.

[0050] Comparative Example 7

[0051] Prepare the polyurethane foam according to the method of Example 1, but replace the reactive catalyst PC-31 with the catalyst A-33 in equal mass.

[0052] Comparative Example 8

[0053] Prepare the polyurethane foam according to the method of Example 1, but replace the reactive catalyst PC-37 with the catalyst A-33 in equal mass.

[0054] The test results show that the dimensional shrinkage rates (135 °C, 48 hours) of the polyurethane foam materials in Comparative Example 5 - Comparative Example 8 are 4.6%, 5.7%, 4.4%, and 4.2% respectively. It can be seen that only by adding the reactive catalyst PC-31 and the reactive catalyst PC-37 simultaneously can the high-temperature dimensional stability of the polyurethane foam material be significantly improved.

[0055] The above are only the preferred embodiments of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions falling within the concept of the present invention belong to the protection scope of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements should also be regarded as within the protection scope of the present invention.

Claims

1. A fully water-open-cell high-temperature resistant polyurethane foam product for a food fermentation tank, characterized in that: The invention is made of component A and component B, and the mass ratio of component A to component B is 100:100-105; component A is composed of the following components in parts by weight: 100 parts of melamine polyether polyol, 10-25 parts of halogen-free flame retardant, 1-2 parts of foam stabilizer, 0.5-1.5 parts of cell opener, 0.5-2 parts of catalyst composition, and 3-4 parts of deionized water; component B is polymethyl polyphenyl polyisocyanate PM-400 with a functionality greater than 2.

2.

2. The all-water open-cell high-temperature resistant polyurethane foam product for food fermentation tanks according to claim 1, characterized in that: The halogen-free flame retardant is flame retardant TEP.

3. The all-water open-cell high-temperature resistant polyurethane foam product for food fermentation tanks according to claim 1, characterized in that: The foam stabilizer is silicone oil Niax Y-16429.

4. The all-water open-cell high-temperature resistant polyurethane foam product for food fermentation tanks according to claim 1, characterized in that: The cell opening agent is ORTEGOL 501.

5. The all-water open-cell high-temperature resistant polyurethane foam product for food fermentation tanks according to claim 1, characterized in that: The catalyst composition is a composition of reactive catalyst PC-37 and reactive catalyst PC-31.

6. The all-water open-cell high-temperature resistant polyurethane foam product for food fermentation tanks according to claim 1, characterized in that: Melamine polyether polyol is prepared by ring-opening polymerization of melamine formaldehyde resin and propylene oxide under catalyst conditions, and has a functionality of 4 and a hydroxyl value of 300 mgKOH / g.

7. The all-water open-cell high-temperature resistant polyurethane foam product for food fermentation tanks according to claim 1, characterized in that: It is made of component A and component B, and the mass ratio of component A to component B is 100:100; component A is composed of the following ingredients in parts by weight: 100 parts of melamine polyether polyol, 20 parts of halogen-free flame retardant TEP, 1.8 parts of silicone oil Niax Y-16429, 0.8 parts of ORTEGOL 501, 0.8 parts of reactive catalyst PC-37, 0.2 parts of reactive catalyst PC-31, and 3.5 parts of deionized water; component B is polymethyl polyphenyl polyisocyanate PM-400 with a functionality greater than 2.

2.

8. A method for preparing a fully water-open-cell high temperature resistant polyurethane foam product for a food fermentation tank according to any one of claims 1 to 7, characterized in that: The components of component A are put into a container in proportion and stirred evenly to obtain component A; then components A and B are mixed according to a mass ratio and foamed by a high-pressure foaming machine to obtain a full-water open-cell high-temperature resistant polyurethane foam product for food fermentation tanks.