Branched three-dimensional structure triptycene amino polyether polyol as well as preparation method and application thereof

Abstract

The invention discloses triptycene amino polyether polyol with a branched three-dimensional structure as well as a preparation method and application of the triptycene amino polyether polyol. The triptycene amino polyether polyol has a structural expression as shown in the specification; the triptycene amino polyether polyol provided by the invention is applied to preparation of rigid polyurethane foam, a foam structure with uniform pore size distribution and complete foam wall can be generated, and the mechanical property and long-term stability of the foam are improved;

Description

Technical Field

[0001] This invention belongs to the field of polyether polyol technology, specifically relating to a branched stereostructured triterpenoid amino polyether polyol and its preparation method and application. Background Technology

[0002] Rigid polyurethane (PU) foam is one of the main types of polyurethane synthetic materials. It is composed of polyether polyol or polyester polyol reacting with isocyanate to form the polyurethane matrix, and uses CO2 generated by the reaction of isocyanate with water, or a low-boiling-point blowing agent as the initiating gas to make porous foam plastic. This system is suitable for both all-water foaming formulations and formulations containing some non-water blowing agents.

[0003] Water-based rigid polyurethane foam systems using water as the sole or primary blowing agent represent an important approach to addressing environmental issues associated with traditional blowing agents, such as residual chlorine and excessively high global warming potential (GWP). In terms of safety, these foaming systems also offer advantages. The CO2 generated from the reaction of water and isocyanate is an inert gas, reducing the oxygen concentration within the foam cells. When used with flame retardants, the oxygen index (OI) can typically reach over 26% (compared to approximately 22-24% for traditional rigid foam). Furthermore, there is no volatilization or residue of organic blowing agents. At high temperatures or during combustion, only small amounts of CO2 and water vapor are produced, resulting in extremely low toxicological hazards. This makes them suitable for applications with high safety requirements, such as construction, electronics, cold chain logistics, indoor insulation, food cold chain, and automotive components.

[0004] The main technical challenges of water-blown foaming systems are as follows: First, the high water content in water-blown systems leads to significant compatibility issues with the mixture, making the search for polyether polyols or their combinations with good water compatibility crucial for expanding application range. Second, the CO2 generated during water-blowing has a lower saturated vapor pressure and smaller molecular dynamics size compared to low-boiling-point alkane blowing agents, making it easier to escape from the cell cavities. This results in a poorer supporting effect on the cavities, leading to inferior foam performance at the same density. This manifests as weaker mechanical properties such as compressive strength and dimensional stability, as well as poor thermal and mechanical stability during long-term storage. To achieve ideal mechanical properties and insulation effects, a larger foam filling volume is often required, which limits its application in thin-walled products such as freezers, electric water heaters, and car refrigerators.

[0005] Patent CN115246917A discloses a method for preparing ethylene oxide polyether polyol and all-water foam, which can improve the stability and compressive strength of foam in the range of -20℃ to 80℃, but does not address the long-term storage stability of foam; Patent CN116444751B discloses an all-water system rigid polyurethane foam with good mechanical properties and environmental protection, but its thermal conductivity increases significantly after long-term storage, resulting in insufficient long-term stability. Summary of the Invention

[0006] To address the above technical problems, this invention proposes a branched, three-dimensional triterpenoid amino polyether polyol, its preparation method, and its application.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] A branched, stereostructured triterpenoid amino polyether polyol has the structural expression shown below:

[0009]

[0010] In Formula I, n1, n2, n3, n4, n5 and n6 are each independently selected from integers from 1 to 5, for example, they are each independently selected from 1, 2, 3, 4 or 5; R1, R2, R3, R4, R5 and R6 are each independently selected from H or methyl.

[0011] The high-density terminal hydroxyl groups distributed on the molecular chain of the tripterene amino polyether polyol can form strong hydrogen bonds with water and other polyether / polyester polyol molecules, significantly reducing the interfacial tension of multi-component systems and minimizing phase separation. This characteristic makes it suitable for formulations with high water content combined polyether / polyester polyols. During the foaming process, the homogenized mixing system can reduce the viscosity of the foaming material, improve the flow and wettability of the foam liquid, and ensure uniform bubble nucleation rate and controllable bubble growth process. Ultimately, it generates a foam structure with uniform pore size distribution and intact cell walls, improving the mechanical properties of the foam. Furthermore, studies have found that this structure can provide good long-term stability for the foam.

[0012] In some preferred examples, the hydroxyl value of the tripterene amino polyether polyol is 160-460 mgKOH / g, such as 165 mgKOH / g, 210 mgKOH / g, 260 mgKOH / g, 310 mgKOH / g, 340 mgKOH / g, 385 mgKOH / g, 410 mgKOH / g, etc., preferably 165-410 mgKOH / g.

[0013] This invention also provides a method for preparing the branched stereostructured triterpenoid amino polyether polyol as described above, comprising the following steps:

[0014]

[0015] The compound represented by formula a is dissolved in a solvent, and an oxidized olefin is introduced to carry out an autocatalytic addition polymerization reaction to obtain the triterpenoid amino polyether polyol.

[0016] In some preferred examples, the oxidized olefin is ethylene oxide and / or propylene oxide; when the oxidized olefin is a mixture of propylene oxide and ethylene oxide, there is no particular limitation on the ratio of the two, for example, the molar ratio of the two is 2:1, 3:1, 5:1, 1:1, 1:4, etc.

[0017] Preferably, the molar ratio of the compound represented by formula a to the oxidized olefin is 1:(6-42), more preferably 1:(12-36), and even more preferably 1:(12-30).

[0018] In some preferred embodiments, the solvent is one or more of m-cresol, 1-methyl-2-pyrrolidone, N,N,-dimethylformamide, N,N-dimethylacetamide, and tetrahydrofuran;

[0019] Preferably, the molar ratio of the compound represented by formula a to the solvent is 1:(12-28), more preferably 1:(15-25), and even more preferably 1:(17-23).

[0020] In some preferred examples, the reaction temperature is 120-170℃ and the reaction pressure is 0.2-0.6MPa;

[0021] Preferably, the reaction time is 4-20 hours.

[0022] The present invention also provides a rigid polyurethane foam prepared by water foaming using the branched stereostructured tripterene amino ether polyol described above or the branched stereostructured tripterene amino ether polyol prepared by the method described above as raw material.

[0023] The rigid polyurethane foam, through the optimized combination of a branched, three-dimensional structured triterpenoid amino ether polyol blend and catalyst system, effectively promotes the construction of a three-dimensional framework for the polyurethane foam, with high-density terminal hydroxyl groups as the core functional sites. The branched spatial structure enables the polyether polyol molecules to form a denser three-dimensional cross-linked network with isocyanate (-NCO), reducing the spacing between polyurethane polymer chain segments, minimizing network defects, achieving small-pore size and consistent structure, reducing the foam's thermal conductivity (λ value), inhibiting CO2 gas molecules from escaping through the polyurethane pore walls, and preventing later pore structure shrinkage or cracking. This improves the foam's mechanical strength from both "structural construction" and "system stability" dimensions, and unexpectedly, significantly enhances the foam's long-term dimensional stability and aging resistance. Therefore, the rigid polyurethane foam is suitable as a filling material for lightweight equipment housings, automotive structural components (such as door panels, dashboard frames, and car refrigerators), and as an internal filler for refrigeration and insulation products such as electric water heater inner tanks, commercial display cabinets, and car refrigerators.

[0024] In some preferred embodiments, the rigid polyurethane foam comprises the following components in parts by weight:

[0025] a) 100 parts of the mixture,

[0026] b) 0-10 parts of non-aqueous foaming agent

[0027] c) 127-177 parts of isocyanate

[0028] The mixture, based on a total mass of 100 parts, comprises the following raw materials: 85-92 parts of a combined polyol, 2-5 parts of a surfactant, 1-3 parts of a catalyst, and 4-7 parts of water.

[0029] The combined polyols include the branched stereostructured tripterene amino ether polyols described above or the branched stereostructured tripterene amino ether polyols prepared by the method described above.

[0030] Preferably, the non-aqueous foaming agent is selected from one or more of n-pentane (NP), cyclopentane (CP), and isopentane (IP);

[0031] Preferably, the isocyanate is polymeric MDI, more preferably polymeric MDI with an NCO content of 30-32%, and more preferably one or more of Wanhua PM-200, Wanhua PM-2010, and Wanhua PM-400; the amount of isocyanate used is preferably such that the isocyanate index of the rigid polyurethane foam is 1.05-1.55.

[0032] Preferably, the surfactant is selected from at least one of alkali metal salts of fatty acids, fatty alcohol polyoxyethylene ethers, fatty acid quaternary ammonium salts, and siloxane polymers, and more preferably at least one of Momentive's silicone oil Niax L6900, silicone oil Niax L5340, Evonik's silicone oil B8110, and silicone oil B8239F.

[0033] Preferably, the catalyst comprises a foaming catalyst, a gel catalyst and a trimerizing catalyst, and their mass ratio is preferably (0.3-0.6):(0.7-1.7):(0.4-0.5).

[0034] Preferably, the foaming catalyst is selected from one or more of bis(dimethylaminoethyl) ether, pentamethyldiethylenetriamine, and tetramethylhexanediamine.

[0035] Preferably, the gel catalyst is selected from one or more of dimethylbenzylamine, dimethylcyclohexane, [(dialkylamino)alkyl]-trialkylpropylenediamine or triethylenediamine.

[0036] Preferably, the trimerizing catalyst is one or more of potassium acetate, 2-hydroxy-N,N,N-trimethyl-1-propylaminocarbamate, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine.

[0037] In some preferred examples, the combined polyol comprises the following components:

[0038] Triptene amino polyether polyol I 30-50 parts

[0039] 0-20 parts of polyether polyol II with palm oil as the starting agent;

[0040] Polyether polyol III with diethylene glycol as the initiator: 14.6-39 parts;

[0041] 5-20 parts of polyester polyol IV with terephthalic acid as the initiator;

[0042] Preferably, the hydroxyl value of the polyether polyol II with palm oil as the initiator is 410-470 mgKOH / g, for example, 410 mgKOH / g, 430 mgKOH / g, or 470 mgKOH / g, and it is prepared by an addition reaction of palm oil with propylene oxide.

[0043] Preferably, the hydroxyl value of the polyether polyol III with diethylene glycol as the initiator is 100-225 mgKOH / g, for example, 100 mgKOH / g, 145 mgKOH / g, 185 mgKOH / g, or 225 mgKOH / g, and it is prepared by an addition reaction of diethylene glycol with propylene oxide.

[0044] The hydroxyl value of polyester polyol IV, which uses terephthalic acid as an initiator, is 120-220 mgKOH / g, for example, 120 mgKOH / g, 150 mgKOH / g, 180 mgKOH / g, 200 mgKOH / g, and 220 mgKOH / g. It is prepared by adding terephthalic acid to propylene oxide.

[0045] The present invention also provides a method for preparing rigid polyurethane foam as described above, characterized by comprising the following steps:

[0046] A mixture is prepared by uniformly mixing a combination of polyols, surfactants, catalysts and water, and then uniformly mixing the mixture with an optional non-aqueous foaming agent. The mixture and isocyanate are then injected into a mold using a high-pressure foaming machine to obtain rigid polyurethane foam.

[0047] Preferably, the operating conditions of the foaming machine are: material temperature 18-22℃, operating pressure 110-160 bar.

[0048] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0049] (1) The tripterene amino ether polyol provided by the present invention can reduce the reactivity in the early stage of polyurethane foam forming, ensure the flow and filling performance of the foam, improve the performance of the flow end and difficult filling position, and ensure the overall performance distribution, especially the mechanical strength performance. In addition, the tripterene amino ether polyol has more group sites that react with NCO groups, which can increase the overall crosslinking density of polyurethane foam. Moreover, the unique Y-shaped spatial configuration in the structural formula has three-dimensional rigidity characteristics, which can build a dendritic network structure in three-dimensional space and have better structural strength. All of these can enhance the overall skeleton strength of the foam, improve the overall mechanical strength performance of the foam and the long-term dimensional stability of the foam.

[0050] (2) The triterene amino polyether polyol provided by the present invention can retain water molecules nearby through hydrogen bonding, improve the compatibility of polyether polyester mixture with water, ensure the uniformity and clarity of the mixture, and obtain a good finished product appearance; after the polyurethane foam is formed and stabilized, due to the adsorption effect of nitrogen atoms in the structure, carbon dioxide molecules generated during the foaming process can be adsorbed in the closed cell structure of the foam, reducing the outward diffusion of carbon dioxide molecules, ensuring the gas pressure inside the cavity, further forming a supporting effect on the cell structure of the foam, and further enhancing the mechanical strength performance of the foam. Attached Figure Description

[0051] Figure 1 This is a 3D optical microscope magnified image of a cross section of the rigid polyurethane foam prepared in Application Example 1. Detailed Implementation

[0052] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0053] The sources of the main materials and reagents in the following examples and comparative examples are as follows:

[0054] 2,6,14-Triaminotriptene, Tianjin Damao;

[0055] 2,7,14-Triaminotriptene, Shanghai Maclean;

[0056] m-Cresol, Shanghai Aladdin;

[0057] Cyclopentane (CP), Longkou Petrochemical;

[0058] Isopentane (IP), Xuchen Chemical;

[0059] Isocyanate: Wanhua Chemical PM-200;

[0060] Surfactants: Silicone oil B8110, Evonik Shanghai; Silicone oil B8239F, Evonik Shanghai; Silicone oil L5340, Momentive.

[0061] Catalysts: The foaming catalyst is pentamethyldiethylenetriamine, the gel catalyst is [(dialkylamino)alkyl]-trialkylpropylenediamine or triethylenediamine, and the trimerization catalyst is potassium acetate. (Shanghai Evonik)

[0062] Polyether polyol A is a traditional amine polyether in the industry, using o-tolyldiamine as the initiator. The product has a hydroxyl value of 440 mgKOH / g. Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0063] Polyether polyol II-1 uses palm oil as an initiator, and the product has a hydroxyl value of 410 mgKOH / g. It is manufactured by Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0064] Polyether polyol II-2 is a product with palm oil as the initiator and a hydroxyl value of 470 mg KOH / g. It is manufactured by Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0065] Polyether polyol III-1 uses diethylene glycol as an initiator, and the product has a hydroxyl value of 225 mg KOH / g. It is manufactured by Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0066] Polyether polyol III-2 uses diethylene glycol as an initiator, and the product has a hydroxyl value of 100 mg KOH / g. It is manufactured by Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0067] Polyester polyol IV-1 uses terephthalic acid as an initiator, and the product has a hydroxyl value of 220 mgKOH / g. Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0068] Polyester polyol IV-2 uses terephthalic acid as an initiator, and the product has a hydroxyl value of 120 mg KOH / g. It is produced by Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0069] Unless otherwise specified, all reagents used below are of analytical grade.

[0070] Polyurethane foam performance testing methods:

[0071] Overfill rate: The ratio of the difference between the actual injection volume and the mold's appropriate filling volume to the appropriate filling volume.

[0072] The foam core density test shall be conducted in accordance with the standard GB / T 6343-2009;

[0073] The thermal conductivity of foam was tested according to standard GB / T 10295-2008.

[0074] The foam compressive strength test shall be conducted in accordance with the standard GB / T 8813-2020;

[0075] The high and low temperature dimensional deformation value test of foam shall be performed in accordance with the standard GB / T 8811-2008.

[0076]

Example 1

[0077]

[0078] 2,6,14-Triaminotriptene (598 g, 2 mol) and m-cresol (3785 g, 35 mol) were added to a reaction vessel, purged with nitrogen, stirred, and heated. Ethylene oxide 1056 g was then added in a measured amount. The reaction was carried out at 150 °C and 0.3 MPa gauge pressure for 8 h until the pressure no longer decreased, yielding polyether polyol I-1, with the structure shown in Formula I-1. The hydroxyl value of the product was determined to be 410 mg KOH / g using the phthalic anhydride esterification method.

[0079]

Example 2

[0080]

[0081] 2,6,14-Triaminotriptene (598 g, 2 mol) and m-cresol (3785 g, 35 mol) were added to a reaction vessel, purged with nitrogen, stirred, and heated. 1392 g of propylene oxide was then added in a measured amount. The reaction was carried out at 160 °C and 0.4 MPa gauge pressure for 10 h until the pressure no longer decreased, yielding polyether polyol I-2, with the structure shown in Formula I-2. The hydroxyl value of the product was determined to be 340 mg KOH / g using the phthalic anhydride esterification method.

[0082]

Example 3

[0083]

[0084] 2,6,14-Triaminotriptene (598 g, 2 mol) and m-cresol (3785 g, 35 mol) were added to a reaction vessel, purged with nitrogen, stirred, and heated. 2640 g of ethylene oxide was then metered in. The reaction was carried out at 150 °C and 0.3 MPa gauge pressure for 8 h, until the pressure no longer decreased, yielding polyether polyol I-1, with the structure shown in Formula I-3. The hydroxyl value of the product was determined to be 210 mg KOH / g using the phthalic anhydride esterification method.

[0085]

Example 4

[0086]

[0087] 2,6,14-Triaminotriptene (598 g, 2 mol) and m-cresol (3785 g, 35 mol) were added to a reaction vessel, purged with nitrogen, stirred, and heated. 3480 g of propylene oxide was then added in a measured amount. The reaction was carried out at 160 °C and 0.5 MPa gauge pressure for 20 h until the pressure no longer decreased, yielding polyether polyol I-4, with the structure shown in Formula I-4. The hydroxyl value of the product was determined to be 165 mg KOH / g using the phthalic anhydride esterification method.

[0088]

Example 5

[0089]

[0090] 2,7,14-Triaminotriptene (598 g, 2 mol) and m-cresol (3785 g, 35 mol) were added to a reaction vessel, purged with nitrogen, stirred, and heated. 1056 g of ethylene oxide was then added in a measured amount. The reaction was carried out at 150 °C and 0.3 MPa gauge pressure for 8 hours until the pressure no longer decreased, yielding polyether polyol I-5, with the structure shown in Formula I-5. The hydroxyl value of the product was determined to be 410 mg KOH / g using the phthalic anhydride esterification method.

[0091]

Application Example 1

[0092] A rigid polyurethane foam comprising the following components in parts by weight:

[0093] a) 100 parts of the mixture,

[0094] b) 0 parts of non-aqueous foaming agent

[0095] c) 155 parts of Wanhua PM-200 isocyanate.

[0096] The mixture comprises: 89 parts of a combination of polyether polyols (containing 30 parts of polyether polyol I-1, 10 parts of polyether polyol II-1; 39 parts of polyether polyol III-1, and 10 parts of polyester polyol IV-1), 3 parts of a surfactant (silicone oil B8110), 2.0 parts of a catalyst (containing 0.5 parts of a foaming catalyst, 1.0 part of a gelling catalyst, and 0.5 parts of a trimerizing catalyst), and 6.0 parts of water;

[0097] A mixture of polyol, surfactant, catalyst and water is uniformly mixed to obtain a mixture. The mixture is then uniformly mixed with an optional non-aqueous foaming agent. The mixture and isocyanate are injected into a mold using a high-pressure foaming machine to obtain rigid polyurethane foam. The operating conditions of the foaming machine are: material temperature 20°C, operating pressure 140 bar (gauge pressure), filling coefficient of the reaction mixture in the mold 1.2, and demolding time 420 s.

[0098]

Application Example 2-5

[0099] Rigid polyurethane foam was prepared using essentially the same method as in Application Example 1, except that the raw material formulation (parts by weight) is referenced in Table 1.

[0100] Table 1

[0101]

[0102]

[0103]

Comparative Application Example 1

[0104] Rigid polyurethane foam was prepared using essentially the same method as in Application Example 2, except that polyether polyol I-2 was replaced with an equal part by weight of polyether polyol A (hydroxyl value 440 mg KOH / g).

[0105]

Comparative Application Example 2

[0106] Rigid polyurethane foam was prepared using a method essentially the same as in Application Example 5, except that the amount of polyether polyol I-5 was changed to 0 parts and the amount of polyether polyol II-1 was changed to 55 parts.

[0107] The performance tests of the rigid polyurethane foams provided in each application example and comparative application example were performed as shown in Table 2. The results are as follows:

[0108] Table 2

[0109]

[0110]

[0111] Additionally, the rigid polyurethane foam prepared in accordance with Example 1 was observed using a 3D optical microscope at 50x magnification, and its microscopic images are shown below. Figure 1 This indicates that the triterpenoid amino polyether polyol provided by the present invention can significantly reduce the pore size of foam and make the pore size uniform, thus providing good support for the macroscopic mechanical properties and long-term stability of foam.

[0112] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A branched stereoregular trirachyaminopolyether polyol, characterized in that, has a structural expression as shown below: In formula I, n1, n2, n3, n4, n5 and n6 are each independently selected from an integer of 1-5; R1, R2, R3, R4, R5, R6 are each independently selected from H or methyl.

2. The branched stereocomplexed tristar polyamino polyether polyol according to claim 1, wherein, The triptycene aminopolyether polyol has a hydroxyl value of 160-460 mgKOH / g, preferably 165-410 mgKOH / g.

3. A process for the preparation of branched stereoregular trihelical polyether polyol according to claim 1 or 2, characterized by, The method comprises the following steps: The compound represented by formula a is dissolved in a solvent, and an alkylene oxide is introduced to perform autocatalytic addition polymerization to prepare the triptycene aminopolyether polyol.

4. The method for preparing the branched stereostructured triterpenoid amino polyether polyol according to claim 3, characterized in that, The alkylene oxide is ethylene oxide and / or propylene oxide; Preferably, the molar ratio of the compound represented by formula a to the alkylene oxide is 1:(6-42), preferably 1:(12-36), more preferably 1:(12-30).

5. The method for preparing the branched stereostructured triterpenoid amino polyether polyol according to claim 3, characterized in that, The solvent is one or more of m-cresol, 1-methyl-2-pyrrolidone, N,N,-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran; Preferably, the molar ratio of the compound represented by formula a to the solvent is 1:(12-28), preferably 1:(15-25), more preferably 1:(17-23).

6. The method for preparing the branched stereostructured triterpenoid amino polyether polyol according to any one of claims 3-5, characterized in that, The reaction temperature is 120-170℃, and the reaction pressure is 0.2-0.6 MPa; Preferably, the reaction time is 4-20h.

7. A polyurethane rigid foam prepared by water foaming using the branched stereoscopic structure triptycene aminopolyether polyol of claim 1 or 2 or the branched stereoscopic structure triptycene aminopolyether polyol prepared by the method of any one of claims 3-6 as a raw material.

8. The polyurethane rigid foam according to claim 7, characterized in that, The components include the following weight parts: a) mixture 100 parts, b) non-water blowing agent 0-10 parts, c) isocyanate 127-177 parts, The mixture is composed of the following raw materials, including: combined polyol 85-92 parts, surfactant 2-5 parts, catalyst 1-3 parts, water 4-7 parts, with the total mass being 100 parts. The combined polyol comprises the branched stereoscopic structure triptycene aminopolyether polyol of claim 1 or 2 or the branched stereoscopic structure triptycene aminopolyether polyol prepared by the method of any one of claims 3-6. Preferably, the non-water blowing agent is selected from one or more of n-pentane, cyclopentane, isopentane; Preferably, the isocyanate is polymeric MDI, preferably polymeric MDI with an NCO content of 30-32%, more preferably one or more of Wanhua PM-200, Wanhua PM-2010, Wanhua PM-400; Preferably, the surfactant is selected from at least one of alkali metal salt of fatty acid, fatty alcohol polyoxyethylene ether, fatty acid quaternary ammonium salt, and siloxane polymer, preferably at least one of the following: Moment's silicone oil Niax L6900, silicone oil Niax L5340, Wincrete's silicone oil B8110, silicone oil B8239F; Preferably, the catalyst comprises a blowing catalyst, a gelation catalyst, and a trimerization catalyst, preferably in a mass ratio of (0.3-0.6):(0.7-1.7):(0.4-0.5).

9. The polyurethane rigid foam according to claim 7, characterized in that, The combined polyol comprises the following components: Tristar aminopolyether polyol I 30-50 parts, Polyether polyol II with palm oil as initiator 0-20 parts; Polyether polyol III with diethylene glycol as initiator 14.6-39 parts; Polyester polyol IV with terephthalic acid as initiator 5-20 parts; Preferably, the polyether polyol II with palm oil as initiator has a hydroxyl value of 410-470 mgKOH / g, which is prepared by addition reaction of palm oil as initiator and propylene oxide; Preferably, the polyether polyol III with diethylene glycol as initiator has a hydroxyl value of 100-225 mgKOH / g, which is prepared by addition reaction of diethylene glycol as initiator and propylene oxide; The polyester polyol IV with terephthalic acid as initiator has a hydroxyl value of 120-220 mgKOH / g, which is prepared by addition reaction of terephthalic acid as initiator and propylene oxide.

10. A process for the production of a polyurethane rigid foam as claimed in claim 8 or 9, characterized in that, comprising the steps of: mixing the combined polyol, surfactant, catalyst and water to obtain a mixture, mixing the mixture and optionally a non-aqueous blowing agent, injecting the mixture and isocyanate into a mold using a high pressure foaming machine to obtain a polyurethane rigid foam; Preferably, the operating conditions of the foaming machine are: material temperature 18-22 °C, operating pressure 110-160 bar.

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