Hyperbranched polyesteramide polyol, preparation method thereof and application of hyperbranched polyesteramide polyol in rigid polyurethane foam

Abstract

The invention discloses hyperbranched polyesteramide polyol, a preparation method thereof and application of the hyperbranched polyesteramide polyol in rigid polyurethane foam, and relates to the technical field of polyurethane materials. The hyperbranched polyesteramide polyol with high hydroxyl value, high functionality and low viscosity is synthesized by adopting a simple one-pot melt polymerization method; the preparation method is applied to preparation of rigid polyurethane foam. The viscosity of the composite material is reduced by utilizing the three-dimensional branched structure of the hyperbranched polyesteramide polyol, and meanwhile, the crosslinking density is improved through a large number of terminal functional groups so as to enhance the compression strength; the synergistic adjustment of the viscosity and the rigidity of the hyperbranched polyesteramide polyol is realized by regulating and controlling the anhydride containing the benzene ring and the anhydride not containing the benzene ring; polyethylene glycol is introduced to one end of a hyperbranched structure, so that the viscosity of the polyesteramide polyol is further reduced, and meanwhile, the compatibility of the polyesteramide polyol and commercial polyol is improved; water is supplemented to replace part of a physical foaming agent, so that the distribution of molecular chain ureido is regulated and controlled while the environmental protection property is ensured, and foam embrittlement is avoided.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane materials, and in particular to a hyperbranched polyester amide polyol, a preparation method thereof, and application of the hyperbranched polyester amide polyol in rigid polyurethane foam. Background Art

[0002] Polyurethane foam boasts advantages such as low density, light weight, low thermal conductivity, excellent cushioning, and sound absorption and thermal insulation. It is widely used in transportation, packaging, construction, sporting goods, and footwear. Conventional polyurethane foams have insufficient load-bearing capacity and cannot withstand high-load conditions. Furthermore, the viscosity of traditional polyol compositions is too high to meet the requirements of foaming equipment. Conventional methods for increasing the compressive strength of polyurethane foams primarily include particle reinforcement, fiber reinforcement, and structural reinforcement, but each has certain drawbacks: Particle reinforcement technology: Chinese invention patent application publication number CN1900132A discloses a high-strength rigid polyurethane foam. Nanoinorganic materials are incorporated into the formula, improving the material's mechanical properties to a certain extent. However, this particle reinforcement method reduces the rigid foam's toughness and significantly increases the viscosity of the polyol system, making it difficult to disperse the particles and foaming difficult, thus failing to meet processability requirements. Chinese invention patent publication number CN103012738B discloses a method for preparing a rigid polyurethane foam reinforced with modified fly ash microbeads. This method improves the mechanical properties and heat resistance of the polyurethane foam, reduces production costs, and enables the effective use of fly ash. However, fly ash, as the main component of the particle reinforcement, also increases the viscosity of the polyol system, hindering industrial production.

[0003] Fiber reinforcement technology: Chinese invention patent application publication number CN103819651A discloses a high-strength rigid polyurethane foam material. By incorporating a composite reinforcement material, the resulting rigid polyurethane foam exhibits comprehensive improvements in strength and dimensional stability. However, the microparticles in this composite material not only reduce the foam's toughness and increase the viscosity of the polyol composition, but the addition of fibers also increases the density of the foamed product, making it unable to meet lightweighting requirements. Furthermore, the microparticles or fibers introduced by this physical reinforcement method may adversely affect the proper functioning of the foaming equipment.

[0004] Structural Reinforcement: Conventional structural reinforcements mostly use linear polymers as the primary material. These are typically achieved by reacting polyether (or polyester) polyols—polyols with high functional groups, high hydroxyl values, and low molecular weights—with polyisocyanates. These polyols exhibit a dense network structure (i.e., numerous and dense crosslinking points), resulting in foams with high hardness, high compressive strength, and excellent dimensional stability and temperature resistance. However, crosslinked polyols typically have a high viscosity, significantly increasing the viscosity of the polyol system, making it difficult to mix evenly with low-viscosity isocyanates, resulting in an uneven, rigid foam and poor surface quality. Furthermore, high-viscosity polyol systems cannot meet the extraction and atomization requirements of foaming equipment, making them unsuitable for use in large-scale industrial production. Furthermore, increasing the intrinsic crosslinking degree often increases the brittleness of the material system, reducing its flexural and impact resistance, making it difficult to meet practical application requirements. Consequently, conventional polyurethane materials based on linear polymers present an irreconcilable conflict between their mechanical properties and foaming processability. New material structural design approaches are urgently needed to achieve a balanced balance between mechanical and process performance.

[0005] In traditional hyperbranched polyols, the introduction of benzene rings often increases molecular chain rigidity, enhances entanglement, and significantly increases viscosity. For example, Chinese invention patent publication number CN113024441B provides a hyperbranched additive. The benzene rings in the molecular chain lead to poor molecular mobility and a tendency to form solids. Another example is Chinese invention patent application publication number CN118852594A, which provides a hyperbranched polyester polyol with only a single terminal benzene ring. This is controlled by other groups in the molecular chain, resulting in limited strength improvement.

[0006] Therefore, the main technical problem faced by the present invention is to synthesize a hyperbranched polyol with high hydroxyl value, high functionality and low viscosity through molecular structure design and apply it to the preparation of load-bearing / heat-insulating integrated polyurethane foam materials. Summary of the Invention In view of this, the purpose of the present invention is to provide a hyperbranched polyester amide polyol and its preparation method and application in rigid polyurethane foam, aiming to improve the load-bearing capacity of polyurethane foam materials while reducing the viscosity of polyol composition materials to meet the process requirements of foaming equipment. To achieve the above objectives, the present invention provides a load-bearing / insulating integrated polyurethane foam material containing a hyperbranched structure, and also discloses a method for preparing a high-hydroxyl value, high-functionality, low-viscosity polyester amide hyperbranched polyol. The polyurethane foam material is introduced into the polyurethane foam material, and combined with the foam formula design, the compressive strength of the polyurethane foam material is effectively increased, and the overall performance of the foam is improved, which can be applied to thermal insulation scenarios with high load conditions.

[0007] The object of the present invention is achieved through the following technical solutions: <First Aspect> A hyperbranched polyester amide polyol having the general structural formula:

[0008] wherein each R is independently selected from R1 or R2, (N-methylpropionamido), (N-methylphthalimido); Among them, the repeating functional groups corresponding to m, n, x, and y share the same starting position, x=1~10, y=1~10, z=1~20, m=1~10, n=1~10.

[0009] As an embodiment, in the hyperbranched polyester amide polyol structure, the R1 and R2 groups have a relationship in terms of molar number: .

[0010] As an embodiment, in the hyperbranched polyester amide polyol structure, the R1 and R2 groups have a relationship in terms of molar number: .

[0011] As an embodiment, in the hyperbranched polyester amide polyol structural formula, the molar ratio of R1 and R2 groups is 1~4:1.

[0012] As an embodiment, the functionality of the hyperbranched polyester amide polyol is 7.5-16, and the hydroxyl value is 200-420 mgKOH·g -1 , viscosity is 500~1500 mPa·s, molecular weight is 800~5000 g / mol, degree of branching is 0.15~0.66, and moisture content is ≤0.8%.

[0013] As an embodiment, the functionality of the hyperbranched polyester amide polyol is 7.9-10.4, and the hydroxyl value is 320-400 mgKOH·g -1 , viscosity is 600~1200 mPa·s, molecular weight is 1158~2200 g / mol, degree of branching is 0.52~0.54, and moisture content is ≤0.6%.

[0014] As an embodiment, the functionality of the hyperbranched polyester amide polyol is 7.9-9.2, and the hydroxyl value is 320-400 mgKOH·g -1 , viscosity is 600~1000 mPa·s, molecular weight is 1158~1500 g / mol, degree of branching is 0.52~0.54, and moisture content is ≤0.6%.

[0015] As an embodiment, the functionality of the hyperbranched polyester amide polyol is 7.9-9.2, and the hydroxyl value is 320-400 mgKOH·g -1 , viscosity is 700~1000 mPa·s, molecular weight is 1342~1500 g / mol, degree of branching is 0.53~0.54, and moisture content is ≤0.5%.

[0016] As an embodiment, the functionality of the hyperbranched polyester amide polyol is 8-9.2, and the hydroxyl value is 320-380 mgKOH·g -1 , viscosity is 700~900 mPa·s, molecular weight is 1340~1470 g / mol, degree of branching is 0.53~0.54, and moisture content is ≤0.5%.

[0017] In some embodiments, the hyperbranched polyester amide polyol has a functionality of 8.3 to 9.2 and a hydroxyl value of 340 to 380 mgKOH·g -1 , viscosity is 700~800 mPa·s, molecular weight is 1342 g / mol, degree of branching is 0.54, and moisture content is 0.5%.

[0018] In some embodiments, the hyperbranched polyester amide polyol has a functionality of 8 to 9 and a hydroxyl value of 320 to 360 mgKOH·g -1 , viscosity is 800~900 mPa·s, molecular weight is 1470 g / mol, degree of branching is 0.53, and moisture content is 0.4%.

[0019] In some embodiments, the hyperbranched polyester amide polyol has a functionality of 8.3 to 9.2 and a hydroxyl value of 340 to 380 mgKOH·g -1 , viscosity is 700~800 mPa·s, molecular weight is 1340 g / mol, degree of branching is 0.54, and moisture content is 0.5%.

[0020] In some embodiments, the hyperbranched polyester amide polyol has a functionality of 7.9 to 8.7 and a hydroxyl value of 340 to 400 mgKOH·g -1 , viscosity is 900~1000 mPa·s, molecular weight is 1500 g / mol, degree of branching is 0.53, and moisture content is 0.5%.

[0021] In some embodiments, the hyperbranched polyester amide polyol has a functionality of 8.3 to 9.0 and a hydroxyl value of 335 to 375 mgKOH·g -1 , viscosity is 600~700 mPa·s, molecular weight is 1158 g / mol, degree of branching is 0.52, and moisture content is 0.6%.

[0022] In some embodiments, the hyperbranched polyester amide polyol has a functionality of 9.5 to 10.4 and a hydroxyl value of 360 to 400 mgKOH·g -1 , viscosity is 1000~1200 mPa·s, molecular weight is 2200g / mol, degree of branching is 0.54, and moisture content is 0.6%.

[0023] <Second Aspect> A method for preparing a hyperbranched polyester amide polyol comprises the following steps: Under a protective atmosphere, aliphatic alcohol amine monomers, acid anhydride and monomethyl ether polyethylene glycol are stirred and reacted at a first temperature for a first time by heating and reflux, then stirred and reacted at a second temperature for a second time, and cooled to room temperature to obtain the hyperbranched polyester amide polyol.

[0024] As an embodiment, the molar ratio of the aliphatic alcohol amine monomer, the acid anhydride and the monomethyl ether polyethylene glycol is 1: 1: 0.1~0.125.

[0025] In some embodiments, the molar ratio of the acid anhydride to the monomethyl ether polyethylene glycol is 8:1.

[0026] As an embodiment, the aliphatic alcohol amine monomer is one or more of: aminoethylene glycol, aminopropylene glycol, aminobutanediol, aminopentanediol, N,N-bis(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxymethyl)ethylenediamine, N,N-bis(2-hydroxymethyl)methanediamine, N,N-bis(2-hydroxyethyl)methanediamine, and tris(hydroxymethyl)aminomethane.

[0027] In some embodiments, the aliphatic alcoholamine monomer is aminopropylene glycol.

[0028] As an embodiment, the acid anhydride is an acid anhydride with a benzene ring and / or an acid anhydride without a benzene ring.

[0029] As an embodiment, the acid anhydride having a benzene ring is 1,2,4-benzenetricarboxylic anhydride.

[0030] As an embodiment, the acid anhydride without a benzene ring is one or more of: succinic anhydride, glutaric anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, 2,5-dihydroxy-2,5-dioxo-3-furancarboxylic acid, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, 2,5-dihydroxy-4-methyl-2,5-dioxo-3-furancarboxylic acid, α-methyl-cis-aconitic anhydride, and 2,5-dihydroxy-4-methyl-2,5-dioxo-3-furanpropionic acid.

[0031] As an embodiment, the molar fraction of the acid anhydride with a benzene ring in the acid anhydride is 20% to 100%.

[0032] As an embodiment, the molar fraction of the acid anhydride without a benzene ring in the acid anhydride is 50% to 100%.

[0033] As an embodiment, the molar ratio of the acid anhydride with a benzene ring to the acid anhydride without a benzene ring in the acid anhydride is 1:1~4.

[0034] In some embodiments, the acid anhydride includes 1,2,4-benzenetricarboxylic anhydride.

[0035] In some embodiments, the anhydride is 1,2,4-benzenetricarboxylic anhydride and succinic anhydride.

[0036] As an embodiment, the first temperature is 90-120° C., and the first time is 0.5-4 h.

[0037] As an embodiment, the second temperature is 120-240° C., and the second time is 1-8 hours.

[0038] As an embodiment, the second time is 1 to 4 hours.

[0039] In some embodiments, the first temperature is 100° C., and the first time is 1.5 hours.

[0040] In some embodiments, the second temperature is 220-240° C., and the second time is 1-4 hours.

[0041] As an embodiment, the protective atmosphere is nitrogen.

[0042] <Third Aspect> The present invention provides a method for preparing a rigid polyurethane foam containing the hyperbranched polyester amide polyol, comprising the following steps: Mixing component A and stirring for the first time until the mixture is uniform to obtain a polyol composition; adding polyisocyanate to the polyol composition and stirring for a second time at the third temperature to obtain a PU slurry; injecting the PU slurry into a preheated mold for foaming, then treating the PU slurry together with the mold at a fourth temperature and cooling to room temperature to obtain the rigid polyurethane foam; The component A comprises, by mass, 70-120 parts of hyperbranched polyester amide polyol, 20-55 parts of polyether polyol, 0.6-5.0 parts of catalyst, 1-3 parts of foam stabilizer, 5-15 parts of cross-linking agent, 0.5-20 parts of physical foaming agent, 0.5-20 parts of chemical foaming agent, 5-15 parts of flame retardant, and 100-150 parts of polyisocyanate. The mass ratio of the polyisocyanate to the polyol combination is 1-1.2:1.

[0043] As an embodiment, the functionality of the hyperbranched polyester amide polyol is 7.9-9.2, and the hydroxyl value is 320-400 mgKOH·g -1 , viscosity is 600~1000 mPa·s, molecular weight is 1158~1500 g / mol, degree of branching is 0.52~0.54, and moisture content is ≤0.6%.

[0044] As an embodiment, the mass ratio of the hyperbranched polyester amide polyol to the polyether polyol is 7-12:3.

[0045] In some embodiments, the mass ratio of the hyperbranched polyester amide polyol to the polyether polyol is 7:3.

[0046] In some embodiments, the mass ratio of the hyperbranched polyester amide polyol to the polyether polyol is 4:1.

[0047] As an embodiment, the mass ratio of the physical foaming agent to the chemical foaming agent is 1.5~5:1.

[0048] In some embodiments, the mass ratio of the physical foaming agent to the chemical foaming agent is 25:9.

[0049] In some embodiments, the mass ratio of the physical foaming agent to the chemical foaming agent is 7.78:1.56.

[0050] In some embodiments, the mass ratio of the physical foaming agent to the chemical foaming agent is 3.23:2.15.

[0051] As an embodiment, the functionality of the polyether polyol is 4.6-5.8 and the hydroxyl value is 360-400 mgKOH·g -1 , viscosity is 10000~12500 mPa·s.

[0052] In some embodiments, the polyether polyol has a functionality of 4.6 to 5.8 and a hydroxyl value of 360 to 400 mg KOH·g -1 , viscosity is 10000~12500mPa·s.

[0053] As an embodiment, the catalyst is one or more of tetramethylethylenediamine, triethanolamine, triethylenediamine, N,N-dimethylcyclohexylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, pentamethyldiethylenetriamine, triethylenediamine, A-33, PT303, stannous octoate, dibutyltin dilaurate, dibutyltin mercaptan, dibutyltin diacetate, MB20, and butyl titanate.

[0054] In some embodiments, the catalyst is pentamethyldiethylenetriamine and dibutyltin dilaurate.

[0055] As an embodiment, the foam stabilizer is one or more of M-8805, M-8808, M-8809, M-8815, M-8860, M-88308, M-88310, M-88108, M-88109, M-88716, and M-88719.

[0056] In some embodiments, the foam stabilizer is M-88308.

[0057] As an embodiment, the cross-linking agent is one or more of glycerol, pentaerythritol, sorbitol, sucrose, and polyether 403.

[0058] In some embodiments, the crosslinking agent is polyether 403.

[0059] As an embodiment, the physical foaming agent is one or more of HFC-245fa, HFC-134a, HFC-365mfc, HFC-227ea, HCFC-141b, CFC-11, cyclopentane, n-pentane, cycloisopentane, and 3,3-trifluoropropylene.

[0060] In some embodiments, the physical blowing agent is dichloroethylene.

[0061] As an embodiment, the chemical blowing agent is water.

[0062] As an embodiment, the flame retardant is one or more of TCPP, TCEP and TEP.

[0063] In some embodiments, the flame retardant is tris(2-chloropropyl) phosphate.

[0064] As an embodiment, the polyisocyanate has an -NCO content of 30% to 35%, a functionality of 2.5 to 2.9, a viscosity of 150 to 250 mPa·s, and a density of 1.20 to 1.30 g·cm -3 .

[0065] As an embodiment, the stirring speed of the first stirring is 800-2000 r / min and the stirring time is 20-50 min.

[0066] In some embodiments, the stirring speed of the first stirring is 1000 r / min, and the stirring time is 30 min.

[0067] As an embodiment, the stirring speed of the second stirring is 800-2000 r / min, and the stirring time is 10-30 s.

[0068] In some embodiments, the stirring speed of the second stirring is 1000 r / min, and the stirring time is 15 s.

[0069] As an embodiment, the third temperature is 25-35°C.

[0070] As an embodiment, the mold preheating temperature is 40~90°C.

[0071] As an embodiment, the fourth temperature is 60-120° C., and the treatment time is 12-48 hours.

[0072] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a hyperbranched polyesteramide polyol, a preparation method thereof, and its application in rigid polyurethane foam. Through molecular structure design, a simple one-pot melt polymerization method is used to synthesize a high-hydroxyl-value, high-functionality, low-viscosity polyesteramide hyperbranched polyol. This polyurethane foam is then introduced into a polyurethane foam material, resulting in the polyurethane foam having integrated load-bearing and thermal insulation functions, improving the overall performance of the material while meeting the requirements of foaming equipment. This synthesis method has advantages in terms of time and cost, a wide range of raw material sources, and a wide range of raw material sources. This method offers advantages in terms of time and cost, making it easy to implement large-scale industrial production. This is primarily reflected in the following aspects: 1) Synchronous adjustment of viscosity and stiffness of hyperbranched polyester amide polyols Since the benzene ring has structural rigidity, the structural strength of the foam material can be improved by introducing the benzene ring structure. Furthermore, the performance of the desired polyurethane foam material can be further controlled by regulating the proportion and type of monomers required for the hyperbranched polyester amide polyol.

[0073] The present invention regulates the ratio of benzene ring-containing and non-benzene ring-containing acid anhydrides to achieve regulation of N-methylpropionamide groups and N-methylphthalimide groups. This can improve the strength while reducing the viscosity of the hyperbranched polyol, thereby achieving coordinated adjustment of the viscosity and stiffness of the hyperbranched polyester amide polyol and meeting the subsequent demand for balancing the mechanical properties and process performance of rigid polyurethane foam.

[0074] At the same time, by introducing polyethylene glycol at one end of the hyperbranched structure, the viscosity of the polyester amide polyol is further reduced, and the compatibility of the polyester amide polyol with commercial polyols can be improved.

[0075] 2) Environmental breakthrough The ozone depletion potential of water is zero, which completely avoids the damage to the ozone layer and greenhouse effect caused by traditional chlorofluorocarbon foaming agents. The preparation process is green and environmentally friendly, meeting the needs of sustainable development. The hyperbranched structure enables the polyol to maintain low viscosity at a high molecular weight, reducing the viscosity of the combined material and meeting the fluidity requirements of the foaming process without the need for additional solvent adjustment. In addition, the hyperbranched polyester amide polyol is fluid and can be miscible with other components of the combined material under solvent-free conditions and react with isocyanate, avoiding the use of organic solvents and reducing pollution.

[0076] 3) Cost and process advantages The preparation process of the hyperbranched polyol provided by the present invention adopts a simple one-pot melt polymerization method to synthesize the hyperbranched polyol, without the need to add raw materials in batches, and without the need to grind the product into powder after the synthesis, thus saving post-processing time and simplifying the preparation process. At the same time, the raw materials are widely available and low in cost, which has certain advantages in time consumption and cost, and is easy to prepare on a large scale in an industrial scale.

[0077] 4) The role of chemical foaming agents When water is used as the foaming agent, there are the following problems in terms of foam physical properties: ① The foam is brittle and has low strength. When the required foam density is low, a large amount of water is required to react with isocyanate to produce enough CO2. In this way, the foam will become brittle due to excessive urea groups generated by the reaction, and the foam toughness will decrease, and it will be easy to powder and fall off. At the same time, low-density foam (such as <30 kg / m 3 ) is particularly obvious, manifested as insufficient compressive strength and low elongation at break; ② Poor dimensional stability. Since CO2 overflows 10 times faster than air infiltration, negative pressure is easily formed in the foam, causing the foam to shrink and deform easily (especially low-density foam in low temperature or high humidity environments); ③ The closed-pore rate is usually only 90%~92% (the ideal value needs to be >95%), which affects the waterproofness and long-term stability.

[0078] There are the following problems in process performance: ① High system viscosity and poor fluidity. Due to the lack of dilution effect of physical foaming agents, the viscosity of the combined polyether is high, resulting in uneven mixing, coarse bubbles, and incomplete filling (especially in complex molds); ② The reaction is highly exothermic. Without water participating in the endothermic process (e.g., the vaporization of a physical foaming agent can absorb heat), the accumulation of reaction heat can easily cause core burning and cracking.

[0079] Therefore, the present invention partially replaces the physical foaming agent with water to generate urea groups in the molecular chain, thereby increasing the strength and rigidity of the foam and improving the mechanical properties of the polyurethane foam. At the same time, it avoids the above-mentioned problems and is more environmentally friendly, easy to operate, and low-cost.

[0080] 5) The role of hyperbranched polyester amide polyols Hyperbranched polyester amide polyols have a three-dimensional spatial topological structure and a large number of active functional groups, which can give the material excellent strength and special functionality. Its special branched structure gives it low viscosity, a large number of terminal functional groups, a large free volume, non-crystallization, high solubility and other characteristics.

[0081] The hyperbranched structure enables the large number of terminal functional groups on the polyol to significantly increase the cross-linking density of the polyurethane foam, thereby simultaneously improving the compressive strength, wear resistance and temperature resistance; the free volume introduced by the hyperbranched structure improves the toughness and impact resistance of the material, solving the contradiction that high-strength materials are brittle; there are a large number of amide bonds in the hyperbranched polyester amide polyol. On the one hand, the amide bonds act as hard segments, which can further improve the structural rigidity of the foam material. At the same time, the presence of amide bonds provides more intermolecular hydrogen bonds, further improving the temperature resistance of the polyurethane foam. BRIEF DESCRIPTION OF THE DRAWINGS

[0082] Other features, objects and advantages of the present invention will become more apparent upon reading the detailed description of non-limiting embodiments with reference to the following drawings: Figure 1 The hyperbranched polyester amide polyol prepared in Example 1 of the present invention 1 H NMR spectrum; Figure 2 This is a comparison chart of the compressive strength of the rigid polyurethane foams prepared in Examples 8, 9, and 10 of the present invention and Comparative Examples 1 and 2; Figure 3 This is a comparison chart of the compressive strength of the rigid polyurethane foams prepared in Example 8, Example 11, Example 12 and Comparative Example 3 of the present invention; Figure 4 This is a comparison chart of the compressive strength of the rigid polyurethane foams prepared in Examples 8, 13, 14, 15, and 18 of the present invention; Figure 5 This is a comparison chart of the compressive strength of the rigid polyurethane foams prepared in Examples 8, 16 and 17 of the present invention. DETAILED DESCRIPTION

[0083] The present invention will be described in detail below with reference to the examples. The following examples will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that those skilled in the art may make several adjustments and improvements without departing from the scope of the present invention. These all fall within the scope of protection of the present invention.

[0084] For ease of understanding, the abbreviations or nouns mentioned below are first explained: PC-5: pentamethyldiethylenetriamine; T-12: dibutyltin dilaurate; HCFC-141b: dichloromonofluoroethane; TCPP: tris(2-chloropropyl) phosphate.

[0085] This specific embodiment provides a hyperbranched polyester amide polyol, which is a random copolymer and has the general structural formula:

[0086] wherein each R is independently selected from R1 or R2, , ; Among them, x=1~10, y=1~10, z=1~20, m=1~10, n=1~10.

[0087] It should be noted that in the general structural formula, the starting position of the repeating functional groups corresponding to n, x, and y is consistent with the starting position of the repeating functional group corresponding to m, that is, the repeating functional groups corresponding to m, n, x, and y share the same starting position.

[0088] Next, the preparation method of the above-mentioned hyperbranched polyester amide polyol is introduced, and the steps are as follows: Under nitrogen protection, aliphatic alcohol amine monomers, acid anhydrides and monomethyl ether polyethylene glycol are placed in a three-necked round-bottom flask equipped with a condensed water receiving device, and stirred at a first temperature for a first time; then the reaction temperature is increased to a second temperature, the stirring reaction is continued for a second time, and the flask is cooled to room temperature to obtain a hyperbranched polyester amide polyol.

[0089] The preparation method of the hyperbranched polyester amide polyol is described in detail below through Examples 1 to 7, which are listed in Tables 1 to 7.

[0090] Example 1 Table 1

[0091] The hyperbranched polyester amide polyol prepared in this example has a functionality of 8.3 to 9.2 and a hydroxyl value of 340 to 380 mgKOH·g -1 The hyperbranched polyester amide polyol has a viscosity of 700-800 mPa·s, a molecular weight of 1342 g / mol, a degree of branching of 0.54, and a moisture content of 0.5%. It exhibits a high hydroxyl value, high functionality, and low viscosity. The low viscosity is attributed to the reduced hydrogen bonding between the hyperbranched polyester amide polyols after the introduction of monomethyl ether polyethylene glycol (PEG).

[0092] Figure 1 The hyperbranched polyester amide polyol prepared in this embodiment 1 The H NMR spectrum shows that the resonance peaks at 3.65–3.54, 4.40–4.24, 4.11–4.02, and 4.85–4.54 ppm are assigned to the protons on the terminal, linear, and branched methylene groups of the hyperbranched polymer, respectively, confirming its hyperbranched structure.

[0093] In the hyperbranched polyester amide polyol prepared in this example, the ratio of R1 to R2 is 4:1.

[0094] Example 2 Table 2

[0095] The hyperbranched polyester amide polyol prepared in this example has a functionality of 8.0-9.0 and a hydroxyl value of 320-360 mgKOH·g -1 The viscosity is 800-900 mPa·s, the molecular weight is 1470 g / mol, the branching degree is 0.53, and the moisture content is 0.4%. It has the characteristics of high hydroxyl value, high functionality, and low viscosity. However, compared with Example 1, the viscosity is increased to a certain extent.

[0096] In the hyperbranched polyester amide polyol prepared in this example, the ratio of R1 to R2 is 1:1.

[0097] Example 3 Table 3

[0098] The hyperbranched polyester amide polyol prepared in this example has a functionality of 8.3-9.0 and a hydroxyl value of 335-375 mgKOH·g -1 The viscosity is 600-700 mPa·s, the molecular weight is 1158 g / mol, the branching degree is 0.52, and the moisture content is 0.6%. It has the characteristics of high hydroxyl value, high functionality, and low viscosity. Compared with Example 1, the viscosity is further reduced.

[0099] In the hyperbranched polyester amide polyol prepared in this embodiment, R is R1.

[0100] Example 4 Table 4

[0101] The hyperbranched polyester amide polyol prepared in this example has a functionality of 7.9-8.7 and a hydroxyl value of 340-400 mgKOH·g -1The viscosity is 900-1000 mPa·s, the molecular weight is 1500 g / mol, the branching degree is 0.53, and the moisture content is 0.5%. It has the characteristics of high hydroxyl value, high functionality and low viscosity. However, compared with Example 2, the viscosity is further increased.

[0102] In the hyperbranched polyester amide polyol prepared in this embodiment, R is R2.

[0103] Example 5 Table 5

[0104] The hyperbranched polyester amide polyol prepared in this example has a functionality of 9.5-10.4 and a hydroxyl value of 360-400 mgKOH·g -1 The obtained product has a viscosity of 1000-1200 mPa·s, a molecular weight of 2200 g / mol, a degree of branching of 0.54, and a moisture content of 0.6%, and is characterized by a high hydroxyl value, high functionality, and low viscosity. However, compared with Example 1, the second time is prolonged, the polymerization reaction time is prolonged, the molecular weight is significantly increased, and the viscosity increases.

[0105] In the hyperbranched polyester amide polyol prepared in this example, the ratio of R1 to R2 is 4:1.

[0106] Example 6 Table 6

[0107] The only difference between this embodiment and embodiment 1 is that the second temperature is increased to 240°C and the second time is reduced to the lower limit of 1 hour. The functionality of the prepared hyperbranched polyester amide polyol is 8.3-9.2 and the hydroxyl value is 340-380 mgKOH·g -1 The obtained product has a viscosity of 700-800 mPa·s, a molecular weight of 1340 g / mol, a degree of branching of 0.54, and a moisture content of 0.5%. It has the characteristics of high hydroxyl value, high functionality, and low viscosity. This is basically the same as in Example 1. This is because appropriately increasing the second temperature can accelerate the second stage reaction process, achieving the same polymerization effect in a shorter time.

[0108] In the hyperbranched polyester amide polyol prepared in this example, the ratio of R1 to R2 is 4:1.

[0109] Example 7 Table 7

[0110] The hyperbranched polyester amide polyol prepared in this example has a functionality of 8.2 to 9.1 and a hydroxyl value of 330 to 360 mgKOH·g-1 , a molecular weight of 1200 g / mol, a degree of branching of 0.54, and a moisture content of 0.6%, exhibiting high hydroxyl value and high functionality. The hyperbranched polyester amide polyol synthesized in this example does not contain polyethylene glycol groups, resulting in a solid product that is difficult to achieve compatibility with commercial polyols and cannot be foamed.

[0111] Next, the method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared above is introduced, and the steps are as follows: Component A (hyperbranched polyester amide polyol, high-functionality polyether polyol, catalyst, foam stabilizer, cross-linking agent, physical foaming agent, chemical foaming agent, flame retardant) is mixed and stirred for the first time until uniform to obtain a polyol composition; Quickly add component B (polyisocyanate) to the polyol combination and stir for the second time at room temperature to obtain PU slurry; The PU slurry is quickly injected into the preheated mold for foaming, and then placed in an oven together with the mold for treatment and cooled to room temperature.

[0112] The mold is opened, and the white product is peeled off and taken out to obtain a rigid polyurethane foam containing a hyperbranched structure.

[0113] The preparation method of the rigid polyurethane foam containing a hyperbranched structure is described in detail below through Examples 8 to 18.

[0114] Example 8 This embodiment provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 1, specifically: The high-functionality polyether polyol in this embodiment has a functionality of 4.6-5.8 and a hydroxyl value of 360-400 mg KOH·g -1 , viscosity 10000~12500 mPa·s; -NCO content of polyisocyanate is 30~35%, functionality 2.5~2.9, viscosity 150~250 mPa·s, density 1.20~1.30 g / cm 3 .

[0115] The polyether polyol used in this embodiment was purchased from Langfang Huayu Innovation Technology Co., Ltd., brand 380.

[0116] By mass, component A is composed of: Hyperbranched polyester amide polyol: 70 parts; High-functionality polyether polyol: 30 parts; Catalyst: PC-5, 1.8 parts; Catalyst: T-12, 0.6 parts; Foam stabilizer: M-88308, 1.5 parts; Crosslinking agent: polyether 403, 10 parts; Physical blowing agent: HCFC-141b, 5 parts; Chemical foaming agent: deionized water, 1.8 parts; Flame retardant: TCPP, 10 parts.

[0117] Component B is: polyisocyanate, and its mass fraction is the total mass fraction of component A.

[0118] The first stirring parameter was 1000 r / min for 30 min, and the second stirring parameter was 1000 r / min for 15 s.

[0119] The mold was preheated to 60 °C, the PU slurry was poured into the mold and foamed for 1 h, and then moved into a 60 °C oven for 24 h.

[0120] The viscosity of the polyol composition obtained in this embodiment is 900-1000 mPa·s, which can meet the requirements of foaming processability (generally, polyurethane foaming machines require the viscosity of the composite polyether to be ≯1500 mPa·s).

[0121] The rigid polyurethane foam containing a hyperbranched structure prepared in this example has a density of 52 kg / m 3 The thermal conductivity was 0.019 W / (m·K), the compressive strength was 0.82 MPa, the dimensional change rate was 0.22%, and the cells were regular, uniform, and dense. This demonstrates that the rigid polyurethane foam containing a hyperbranched structure prepared in this example is lightweight, has a strong load-bearing capacity, good thermal insulation properties, and excellent dimensional stability.

[0122] Example 9 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 1. The steps are basically the same as those in Example 8, except that: In component A, hyperbranched polyester amide polyol: 80 parts; high-functionality polyether polyol: 20 parts.

[0123] The viscosity of the polyol composition obtained in this example is 800-900 mPa·s, which can meet the foaming process requirements.

[0124] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 53 kg / m 3The thermal conductivity was 0.018 W / (m·K), the compressive strength was 0.84 MPa, the dimensional change rate was 0.21%, and the cells were regular, uniform, and dense. This demonstrates that the rigid polyurethane foam containing a hyperbranched structure prepared in this example is lightweight, has a strong load-bearing capacity, good thermal insulation properties, and excellent dimensional stability.

[0125] Example 10 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 1. The steps are basically the same as those in Example 8, except that: In component A, hyperbranched polyester amide polyol: 20 parts; high-functionality polyether polyol: 80 parts.

[0126] The viscosity of the polyol composition obtained in this embodiment is 4000-6000 mPa·s, which cannot meet the foaming process requirements.

[0127] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 55 kg / m 3 The thermal conductivity is 0.025 W / (m·K), the compressive strength is 0.50 MPa, and the dimensional change rate is 0.29%. The foaming is insufficient, irregular, uneven, and not dense.

[0128] Compared with Example 8, the strength of the rigid polyurethane foam prepared in this example is significantly reduced. The reason is that the content of hyperbranched polyester amide polyol is reduced, which on the one hand leads to an increase in the viscosity of the polymer, affecting the uniform expansion of bubbles during the foaming process. The uneven bubble structure (such as different pore sizes and weak pore walls) will weaken the supporting capacity of the foam, resulting in a decrease in compressive strength; on the other hand, the cross-linking density is reduced and the foam structure strength is low.

[0129] Example 11 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 1. The steps are basically the same as those in Example 8, except that: In component A, the physical foaming agent is 7.78 parts and the chemical foaming agent is 1.56 parts.

[0130] The viscosity of the polyol composition obtained in this example is 800-900 mPa·s, which can meet the foaming process requirements.

[0131] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 53 kg / m 3 The thermal conductivity is 0.018 W / (m·K), the compressive strength is 0.81 MPa, the dimensional change rate is 0.21%, and the bubbles are regular, uniform and dense.

[0132] Compared with Example 8, the water content of the chemical foaming agent is slightly reduced, the viscosity of the combined polyether is slightly reduced, the urea groups generated by the reaction with isocyanate are slightly reduced, the compressive strength is slightly reduced, and the dimensional stability is slightly improved.

[0133] Example 12 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 1. The steps are basically the same as those in Example 8, except that: In component A, physical foaming agent: 3.23 parts; chemical foaming agent: 2.15 parts.

[0134] The viscosity of the polyol composition obtained in this example is 1100-1200 mPa·s, which can meet the foaming process requirements.

[0135] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 52 kg / m 3 , thermal conductivity is 0.020 W / (m·K), compressive strength is 0.83 MPa, dimensional change rate is 0.24%, and the cells are regular, uniform and dense.

[0136] Compared with Example 8, the content of chemical foaming agent water is increased, the viscosity of the combined polyether is increased, the number of urea groups generated by reaction with isocyanate increases, the compressive strength increases, and the dimensional stability is slightly reduced.

[0137] Example 13 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 2. The steps are basically the same as those in Example 8, except that: The viscosity of the polyol composition obtained in this example is 1000-1100 mPa·s, which can meet the foaming process requirements.

[0138] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 55 kg / m 3 The thermal conductivity was 0.020 W / (m·K), the compressive strength was 0.84 MPa, the dimensional change rate was 0.21%, and the cells were regular, uniform, and dense. This demonstrates that the rigid polyurethane foam containing a hyperbranched structure prepared in this example is lightweight, has a strong load-bearing capacity, good thermal insulation properties, and excellent dimensional stability.

[0139] Compared with Example 8, the benzene ring content in the hyperbranched polyester amide polyol synthesized in this example is increased, and thus the compressive strength is increased.

[0140] Example 14 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 3. The steps are basically the same as those in Example 8, except that: The viscosity of the polyol composition obtained in this example is 800-900 mPa·s, which can meet the foaming process requirements.

[0141] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 57 kg / m 3 The thermal conductivity was 0.021 W / (m·K), the compressive strength was 0.75 MPa, the dimensional change rate was 0.25%, and the cells were regular, uniform, and dense. This demonstrates that the rigid polyurethane foam containing a hyperbranched structure prepared in this example is lightweight, has a strong load-bearing capacity, good thermal insulation properties, and excellent dimensional stability.

[0142] Compared with Example 8, the hyperbranched polyester amide polyol synthesized in this example does not contain a benzene ring, resulting in a relatively low compressive strength.

[0143] Example 15 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 4. The steps are basically the same as those in Example 8, except that: The viscosity of the polyol composition obtained in this embodiment is 1100-1200 mPa·s, which can meet the foaming process requirements.

[0144] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 56 kg / m 3 The thermal conductivity was 0.022 W / (m·K), the compressive strength was 0.86 MPa, the dimensional change rate was 0.20%, and the cells were regular, uniform, and dense. This demonstrates that the rigid polyurethane foam containing a hyperbranched structure prepared in this example is lightweight, has a strong load-bearing capacity, good thermal insulation properties, and excellent dimensional stability.

[0145] Compared with Example 8, the hyperbranched polyester amide polyol synthesized in this embodiment contains only anhydrides with benzene rings. The benzene rings increase chain rigidity and reduce segment motion. At the same time, physical cross-linking points may be formed due to π-π stacking, thereby increasing viscosity and increasing strength due to rigid groups.

[0146] Example 16 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 5. The steps are basically the same as those in Example 8, except that: The viscosity of the polyol composition obtained in this example is 2400-2500 mPa·s, which cannot meet the process requirements of the foaming equipment.

[0147] The rigid polyurethane foam containing a hyperbranched structure prepared in this example has a density of 55 kg / m 3 The thermal conductivity is 0.029 W / (m·K), the compressive strength is 0.63 MPa, the dimensional change rate is 0.30%, the foaming is insufficient, and the cells are irregular, uneven, and not dense.

[0148] However, compared with Example 8, the molecular weight of the hyperbranched polyester amide polyol synthesized in this example is significantly increased, and the viscosity is increased, which affects the uniform expansion of bubbles during the foaming process. The uneven bubble structure (such as different pore sizes and weak pore walls) will weaken the supporting capacity of the foam, resulting in a decrease in compressive strength, which cannot well meet the foaming process requirements.

[0149] Example 17 This example provides a method for preparing a rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 6. The steps are basically the same as those in Example 8, and the foam properties are also basically the same as those in Example 8. The density is 51 kg / m 3 The thermal conductivity was 0.018 W / (m·K), the compressive strength was 0.83 MPa, the dimensional change rate was 0.21%, and the cells were regular, uniform, and dense. This demonstrates that the rigid polyurethane foam containing a hyperbranched structure prepared in this example is lightweight, has a strong load-bearing capacity, good thermal insulation properties, and excellent dimensional stability.

[0150] Example 18 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 7. The steps are basically the same as those in Example 8, except that: The viscosity of the polyol composition obtained in this example is that of a suspension, and the hyperbranched polyester amide polyol is suspended in the composition in the form of particles. It is almost incompatible with commercial polyols and does not meet the process requirements of the foaming equipment (the presence of solids in the composition may cause blockage or wear of the equipment metering pump, shortening the service life of the equipment). It also affects the apparent quality and physical and chemical properties of the foam.

[0151] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 56 kg / m 3 The thermal conductivity was 0.025 W / (m·K), the compressive strength was 0.48 MPa, the dimensional change rate was 0.28%, and the cells were irregular, non-uniform, and not dense. Compared with Example 8, the rigid polyurethane foam containing a hyperbranched structure prepared in this example had weaker load-bearing capacity, poorer thermal insulation performance, and poorer dimensional stability.

[0152] Comparative Example 1 This embodiment provides a method for preparing a rigid polyurethane foam without hyperbranched polyester amide polyol. The steps are basically the same as those in Example 8, except that: Component A contains 100 parts of high-functionality polyether polyol and does not contain hyperbranched polyester amide polyol.

[0153] In this embodiment, the viscosity of the polyol composition is 5000-8000 mPa·s, and the density of the prepared rigid polyurethane foam is 50 kg / m 3 The thermal conductivity is 0.024 W / (m·K), the compressive strength is 0.45 MPa, the dimensional change rate is 0.30%, the foaming is insufficient, irregular, uneven, and not dense.

[0154] Compared with Example 8, the strength of the rigid polyurethane foam prepared in this example is significantly reduced. The reason is that it does not contain hyperbranched polyester amide polyol. On the one hand, it leads to an increase in the viscosity of the polymer, affecting the uniform expansion of bubbles during the foaming process. The uneven bubble structure (such as different pore sizes and weak pore walls) will weaken the supporting capacity of the foam, resulting in a decrease in compressive strength; on the other hand, the cross-linking density is low and the foam structure strength is low.

[0155] Comparative Example 2 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 1. The steps are basically the same as those in Example 8, except that: In component A, the hyperbranched polyester amide polyol accounts for 30 parts and the high-functionality polyether polyol accounts for 70 parts.

[0156] In this embodiment, the viscosity of the polyol composition is 3000-5000 mPa·s, which cannot meet the process requirements of the foaming equipment.

[0157] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 53 kg / m 3 The thermal conductivity is 0.023 W / (m·K), the compressive strength is 0.54 MPa, the dimensional change rate is 0.28%, the foaming is insufficient, irregular, uneven, and not dense.

[0158] Compared with Example 8, the strength of the rigid polyurethane foam prepared in this example is significantly reduced. The reason is that the content of hyperbranched polyester amide polyol is reduced, which on the one hand leads to an increase in the viscosity of the polymer, affecting the uniform expansion of bubbles during the foaming process. The uneven bubble structure (such as different pore sizes and weak pore walls) will weaken the supporting capacity of the foam, resulting in a decrease in compressive strength; on the other hand, the cross-linking density is reduced and the foam structure strength is low.

[0159] Comparative Example 3 This example provides a method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol prepared in Example 1. The steps are basically the same as those in Example 8, except that: In component A, the physical foaming agent: HCFC-141b is 14 parts, and the chemical foaming agent deionized water is not contained.

[0160] In this embodiment, the viscosity of the polyol composition is 700-800 mPa·s, which can meet the foaming process requirements.

[0161] The rigid polyurethane foam containing hyperbranched structure prepared in this example has a density of 45 kg / m 3 , thermal conductivity is 0.020 W / (m·K), compressive strength is 0.70 MPa, dimensional change rate is 0.20%, and the pores are regular, uniform and dense.

[0162] Compared with Example 8, in this example, except for a small amount of water in the synthesized hyperbranched polyester amide polyol, no additional water reacts with isocyanate to form urea groups. At the same time, the HCFC-141b volatilized during the foaming process requires corresponding tail gas treatment to avoid environmental pollution.

[0163] Performance testing methods The rigid polyurethane foam prepared in the present invention was tested using the following method: Apparent core density: The density of the foam was measured according to GB / T 6343-2009. The size was 100 mm × 100 mm × 50 mm. Five samples were grouped together and the average value was taken.

[0164] Compression Performance Test: Foam plastics were cut into samples measuring 100 mm × 100 mm × 50 mm. Compression performance tests were conducted on an electronic universal testing machine according to GB / T 8813-2008. The compression rate was 5 mm / min. Five samples were grouped together, and the data were averaged. Figures 2 to 5 The following is a comparison chart of the compressive strength of the samples prepared in various embodiments and comparative examples.

[0165] Dimensional stability test: The dimensional stability of the foam was tested according to GB / T 8811-2008. The size specification was 100 mm × 100 mm × 25 mm. Three samples were grouped together and the data were averaged.

[0166] Thermal conductivity test: The thermal conductivity of foam was tested according to GB / T 3399-1982. The size was 40 mm × 40 mm × 5 mm. Two samples were grouped together and the data were averaged.

[0167] In summary, the present invention synthesizes a high-hydroxyl value, high-functionality, low-viscosity polyester amide hyperbranched polyol through molecular structure design and a simple one-pot melt polymerization method, and introduces it into a polyurethane foam material, effectively improving the compressive strength of the polyurethane foam material, so that the polyurethane foam has an integrated load-bearing / insulating function, improving the overall performance of the material, and meeting the requirements of the foaming equipment. It can be applied to insulation scenarios with high-load conditions. This synthesis method has a wide source of raw materials and low cost, has certain advantages in time and cost, and is easy to achieve large-scale industrial preparation.

[0168] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various variations or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A hyperbranched polyester amide polyol, characterized in that The general structural formula is: wherein each R is independently selected from R1 or R2, , ; Among them, the repeating functional groups corresponding to m, n, x, and y share the same starting position, x=1~10, y=1~10, z=1~20, m=1~10, n=1~10.

2. The hyperbranched polyester amide polyol according to claim 1, wherein The functionality of the hyperbranched polyester amide polyol is 7.5-16, and the hydroxyl value is 200-420 mgKOH·g -1 , viscosity is 500~1500 mPa·s, molecular weight is 800~5000, degree of branching is 0.15~0.66, and moisture content is ≤0.8%.

3. A method for preparing a hyperbranched polyester amide polyol according to claim 1 or 2, characterized in that: The following steps are involved: Under a protective atmosphere, aliphatic alcohol amine monomer, acid anhydride and monomethyl ether polyethylene glycol in a molar ratio of 1:1:0.1-0.125 are stirred and reacted at 90-120°C for 0.5-4 hours by heating under reflux, then stirred and reacted at a reaction temperature of 120-240°C for 1-8 hours, and cooled to room temperature to obtain the hyperbranched polyester amide polyol, wherein the acid anhydride is a phenyl ring-containing acid anhydride and / or a phenyl ring-free acid anhydride.

4. The method according to claim 3, characterized in that Also includes at least one of the following technical features: A1. The aliphatic alcoholamine monomer is one or more of: aminoethylene glycol, aminopropylene glycol, aminobutanediol, aminopentanediol, N,N-bis(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxymethyl)ethylenediamine, N,N-bis(2-hydroxymethyl)methanediamine, N,N-bis(2-hydroxyethyl)methanediamine, and tris(hydroxymethyl)aminomethane; B1. The phenyl ring-containing anhydride is: 1,2,4-benzenetricarboxylic anhydride; C1. The non-benzene-containing anhydride is one or more of succinic anhydride, glutaric anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, 2,5-dihydroxy-2,5-dioxo-3-furancarboxylic acid, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, 2,5-dihydroxy-4-methyl-2,5-dioxo-3-furancarboxylic acid, α-methyl-cis-aconitic anhydride, and 2,5-dihydroxy-4-methyl-2,5-dioxo-3-furanpropionic acid.

5. The method according to claim 3, characterized in that Also includes at least one of the following technical features: A2, the molar fraction of the acid anhydride with a benzene ring in the acid anhydride is 20% to 100%; B2, the molar fraction of the acid anhydride without a benzene ring in the acid anhydride is 50% to 100%; C2, the molar ratio of the acid anhydride with a benzene ring to the acid anhydride without a benzene ring in the acid anhydride is 1: 1~4.

6. The method for preparing rigid polyurethane foam using the hyperbranched polyester amide polyol according to claim 1 or 2, wherein: The following steps are involved: Mixing component A and stirring for the first time until the mixture is uniform to obtain a polyol composition; adding polyisocyanate to the polyol composition and stirring for a second time at the third temperature to obtain a PU slurry; injecting the PU slurry into a preheated mold for foaming, then treating the PU slurry together with the mold at a fourth temperature and cooling to room temperature to obtain the rigid polyurethane foam; The component A comprises, by mass, 70-120 parts of hyperbranched polyester amide polyol, 20-55 parts of polyether polyol, 0.6-5.0 parts of catalyst, 1-3 parts of foam stabilizer, 5-15 parts of cross-linking agent, 0.5-20 parts of physical foaming agent, 0.5-20 parts of chemical foaming agent, and 5-15 parts of flame retardant; The polyisocyanate is 100 to 150 parts; The mass ratio of the polyisocyanate to the polyol combination is 1-1.2:1; The mass ratio of the hyperbranched polyester amide polyol to the polyether polyol is 7-12:3; The mass ratio of the physical foaming agent to the chemical foaming agent is 1.5-5:1; The functionality of the hyperbranched polyester amide polyol is 7.9-9.2, and the hydroxyl value is 320-400 mgKOH·g -1 , viscosity is 600~1000 mPa·s, molecular weight is 1158~1500 g / mol, degree of branching is 0.52~0.54, and moisture content is ≤0.6%.

7. The method according to claim 6, characterized in that It also includes one or more of the following technical features: A3. The functionality of the polyether polyol is 4.6-5.8, and the hydroxyl value is 360-400 mgKOH·g -1 , viscosity is 10000~12500mPa·s; B3. The chemical foaming agent is water.

8. The method according to claim 6, characterized in that It also includes one or more of the following technical features: A4. The catalyst is one or more of tetramethylethylenediamine, triethanolamine, triethylenediamine, N,N-dimethylcyclohexylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, pentamethyldiethylenetriamine, triethylenediamine, A-33, PT303, stannous octoate, dibutyltin dilaurate, dibutyltin mercaptan, dibutyltin diacetate, MB20, and butyl titanate; B4. The foam stabilizer is one or more of M-8805, M-8808, M-8809, M-8815, M-8860, M-88308, M-88310, M-88108, M-88109, M-88716, and M-88719; C4, the cross-linking agent is one or more of glycerol, pentaerythritol, sorbitol, sucrose, and polyether 403; D4, the physical foaming agent is one or more of HFC-245fa, HFC-134a, HFC-365mfc, HFC-227ea, HCFC-141b, CFC-11, cyclopentane, n-pentane, cycloisopentane, and 3,3-trifluoropropylene; E4, the flame retardant is one or more of TCPP, TCEP and TEP; F4, the polyisocyanate has an -NCO content of 30% to 35%, a functionality of 2.5 to 2.9, a viscosity of 150 to 250 mPa·s, and a density of 1.20 to 1.30 g·cm -3 .

9. The method according to claim 6, characterized in that It also includes one or more of the following technical features: A5, the stirring speed of the first stirring is 800~2000 r / min, and the stirring time is 20~50 min; B5, the stirring speed of the second stirring is 800~2000 r / min, and the stirring time is 10~30 s; C5, the third temperature is 25-35°C; D5. The mold preheating temperature is 40~90℃; E5. The fourth temperature is 60-120° C., and the treatment time is 12-48 h.

10. A rigid polyurethane foam, characterized in that It is prepared according to the method according to any one of claims 6 to 9.

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