Polymer polyester polyol as well as preparation method and application thereof

Abstract

The invention provides polymer polyester polyol as well as a preparation method and application thereof. The polymer polyester polyol is prepared from the following raw materials in percentage by weight: 60%-89.8% of polyester polyol, 5%-30% of polyester modified acrylic monomers, 5%-30% of other monomers containing vinyl, 0.05%-1% of an initiator and 0.1%-1% of a chain transfer agent. The polymer polyester polyol disclosed by the invention can be well dispersed to form a uniform and stable mixture without adopting a dispersing agent, and the obtained polymer polyester polyol product is moderate in storage stability and viscosity and simple in process; when the polymer polyester polyol is applied to the fields of elastomers such as polyester system flexible foam and soles, remarkable modification and density reduction effects can be achieved, the bearing performance and the dimensional stability of low-density products are greatly improved, and meanwhile, the consumption of traditional vinyl monomers is reduced, so that the POP odor is greatly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of production and application of chemical raw materials, and relates to a polymer polyester polyol and a preparation method and application thereof. Background Art

[0002] Polymer polyol (POP) is a modified polyol product in which polymer particles are dispersed in polyols. Among them, polymer polyols containing vinyl monomers are currently the most widely used. They have two major functions: one is the pore-opening effect; the other is the strengthening effect. It can enhance the modulus of the product while keeping the physical and mechanical properties of other aspects of the product basically unchanged, so it is widely used in polyurethane materials. Since polyester polyurethane systems have better mechanical properties, solvent resistance, oil resistance and other properties, they are widely used in relatively demanding fields. Especially in the field of polyurethane sole microporous elastomers. The current contradiction faced by polyurethane sole products is to reduce density and cost while maintaining dimensional stability and beautiful appearance, and polyester polymer polyols greatly meet the requirements of polyurethane sole products.

[0003] Traditional POP is a modified polyester polyol made by grafting and polymerizing vinyl monomers with polyester polyols as the matrix. It not only maintains the original flexibility of the polyester polyol main chain, but also has the characteristics of vinyl polymer side chains such as rigidity and flame retardancy, thereby improving the physical properties of polyurethane products and expanding the application range of polyurethane soles. Polymer polyester polyol is a dispersion formed by the polymerization of vinyl monomers in carrier polyester polyols. It contains three types of polymers: 1) unmodified polyester polyols (carrier polyester polyols); 2) copolymers and homopolymers of vinyl mixed monomers; 3) vinyl copolymers grafted with carrier polyester polyols. Therefore, the polyester polyols used as POP carriers are required to have basic properties suitable for sole stock products, good compatibility with copolymers and homopolymers of vinyl mixed monomers, and the function of grafting with vinyl copolymers.

[0004] Maleic anhydride or fumaric acid is used as the donor of unsaturated bonds in dispersants in EP0250351 and CN1683425A, and the preparation is relatively cumbersome. Due to the poor activity of the tertiary carbon double bond, the dispersion effect in the polymerization reaction is poor, and the dispersant will also cause the tensile and tearing properties of the product to decrease. CN111100251A adopts a block strategy to prepare a dispersant using the molecular chains of polyether and polyester, ensuring that the dispersant has compatibility with polyester and acrylate fillers, reducing the situation that the traditional dispersant has a small molecular weight, high viscosity, and uneven distribution of double bonds due to polyester, but the dispersant preparation process is relatively complicated. At the same time, although the polyol is devolatilized in the later stage, there will still be a small amount of unreacted vinyl monomers remaining, resulting in odor problems in the polyol, which is unfavorable to the physical and mental health of personnel. Summary of the invention

[0005] In view of the deficiencies of the prior art, the purpose of the present invention is to provide a polymer polyester polyol and a preparation method and application thereof. The polymer polyester polyol of the present invention can achieve good dispersion without using a dispersant to form a uniform and stable mixture. The obtained polymer polyester polyol product has storage stability and moderate viscosity, and the process is simple. The polymer polyester polyol is used in the field of polyester system soft foam, soles and other elastomers to achieve significant modification and density reduction effects, greatly improving the load-bearing capacity and dimensional stability of low-density products. At the same time, the use of traditional vinyl monomers is reduced, resulting in a great improvement in the odor of POP.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a polymer polyester polyol, wherein the raw materials for preparing the polymer polyester polyol include the following components in weight percentage:

[0008]

[0009]

[0010] In the present invention, polyester-modified acrylic monomers are used to replace part of the traditional monomers containing vinyl, so that the polyester-modified acrylic monomers can be well dispersed in the polyester polyols by relying on the polyester structure and a certain number of hydroxyl groups of the polyester-modified acrylic monomers themselves to form a uniform and stable mixture, and thus can have a good dispersion effect without the need for other dispersants. The obtained polymer polyester polyol products have storage stability, moderate viscosity, and simple process. The polymer polyester polyols can be used in the field of polyester system soft foam, soles and other elastomers to achieve significant modification and density reduction effects, greatly improving the load-bearing capacity and dimensional stability of low-density products. At the same time, the use of traditional vinyl monomers is reduced, resulting in a great improvement in POP odor.

[0011] In the present invention, the content of polyester polyol in the raw material for preparing the polymer polyester polyol can be 60%, 63%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, 88% or 89%, the content of the polyester modified acrylic monomer can be 5%, 8%, 10%, 12%, 15%, 18%, 20%, 23%, 25%, 28% or 30%, and the content of other monomers containing vinyl groups can be 5%, 8%, 10%, 12%, 15%, 18%, 20%, 23%, 25%, 28% or 30%. The content of the monomer can be 5%, 8%, 10%, 12%, 15%, 18%, 20%, 23%, 25%, 28% or 30%, the content of the initiator can be 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8% or 1%, and the content of the chain transfer agent can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%.

[0012] Preferably, the number average molecular weight of the polyester polyol is 1000-4000 g / mol, for example 1000 g / mol, 1200 g / mol, 1500 g / mol, 1800 g / mol, 2000 g / mol, 2300 g / mol, 2500 g / mol, 2800 g / mol, 3000 g / mol, 3300 g / mol, 3500 g / mol, 3800 g / mol or 4000 g / mol.

[0013] Preferably, the polyester polyol is a white viscous liquid with an acid value of less than 3 mgKOH / g, for example, 2.8 mgKOH / g, 2.5 mgKOH / g, 2.3 mgKOH / g, 2 mgKOH / g, 1.8 mgKOH / g, 1.5 mgKOH / g, 1.0 mgKOH / g, etc.

[0014] Preferably, the polyester polyol has a viscosity of 1500-6000 mPa.s at 40° C., for example 1500 mPa.s, 1800 mPa.s, 2000 mPa.s, 2500 mPa.s, 3000 mPa.s, 3500 mPa.s, 4000 mPa.s, 4500 mPa.s, 5000 mPa.s, 5500 mPa.s or 6000 mPa.s.

[0015] Preferably, the polyester polyol is prepared by polycondensation of a diol and a dicarboxylic acid or anhydride.

[0016] Preferably, the diol is selected from any one of ethylene glycol, diethylene glycol, 1,4-butanediol or 2-methyl-1,3-propanediol, or a combination of at least two thereof.

[0017] Preferably, the dicarboxylic acid is selected from any one of adipic acid, oxalic acid, succinic acid, glutaric acid or azelaic acid, or a combination of at least two thereof.

[0018] Preferably, the acid anhydride is selected from any one or a combination of at least two of succinic anhydride, adipic anhydride, azelaic anhydride, isophthalic anhydride, phthalic anhydride or hexahydrobiphenyl.

[0019] Preferably, the polyester-modified acrylic monomer is selected from one or a combination of at least two of caprolactone-modified (meth)acrylate, caprolactone-modified hydroxyethyl methacrylate, caprolactone-modified hydroxypropyl acrylate or caprolactone-modified hydroxypropyl methacrylate.

[0020] Preferably, the polyester-modified acrylic monomer has the following structure:

[0021]

[0022] wherein n is selected from an integer of 2-5, for example 2, 3, 4 or 5.

[0023] Preferably, the other vinyl-containing monomers are selected from one or a combination of at least two of styrene, acrylonitrile, butadiene, methyl styrene, ethyl styrene, acrylic acid, acrylic acid ester or methyl methacrylate.

[0024] Preferably, the initiator is selected from benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, tert-amyl peroxide 2-ethylhexyl acid ester, tert-butyl peroxide 2-ethylhexyl acid ester, 1,1'-bis(tert-amyl peroxy)cyclohexane, 1,1'-bis(tert-butyl peroxy)-3,3,5-trimethylcyclohexane, tert-amyl peroxyacetate, tert-amyl peroxybenzoate, tert-butyl peroxy 3,5,5'trimethylhexanoate or tert-butyl peroxybenzoate, or a combination of at least two thereof.

[0025] Preferably, the chain transfer agent is selected from mercaptan compounds.

[0026] Preferably, the thiol compound is selected from one or a combination of at least two of isopropyl alcohol, dodecyl mercaptan, isopentyl mercaptan or hexadecanethiol.

[0027] In a second aspect, the present invention provides a method for preparing the polymer polyester polyol as described in the first aspect above, the preparation method comprising the following steps:

[0028] Material A is added to material B to react to obtain the polymer polyester polyol.

[0029] The material A contains polyester-modified acrylic monomers, other monomers containing vinyl groups, an initiator and polyester polyols, and the material B is polyester polyols.

[0030] Preferably, the material A is added to the material B in a dropwise manner.

[0031] Preferably, material A is added dropwise to material B within 1.5-3 hours (eg, 1.5 hours, 1.8 hours, 2 hours, 2.3 hours, 2.5 hours, 2.8 hours or 3 hours).

[0032] Preferably, the reaction temperature is 110°C-130°C, such as 110°C, 115°C, 118°C, 120°C, 125°C, 128°C or 130°C, and the reaction time is 0.3-3h.

[0033] Preferably, the reaction is carried out under nitrogen protection.

[0034] Preferably, the reaction is carried out at a pressure of 0.20-0.4 MPa, such as 0.2 MPa, 0.22 MPa, 0.25 MPa, 0.28 MPa, 0.3 MPa, 0.33 MPa, 0.35 MPa, 0.38 MPa or 0.4 MPa.

[0035] In the present invention, after the reaction is completed, the pressure is reduced to remove most of the unreacted monomers, and the discharged material is sealed and stored.

[0036] In a third aspect, the present invention provides a polyurethane prepared from the polymer polyester polyol and isocyanate as described in the first aspect.

[0037] In a fourth aspect, the present invention provides a use of the polymer polyester polyol as described in the first aspect or the polyurethane as described in the third aspect in the preparation of a polyurethane elastomer product.

[0038] Preferably, the polyurethane elastomer products include polyurethane soles, polyurethane soft foams and the like.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] The polymer polyester polyol of the present invention can be well dispersed without using a dispersant to form a uniform and stable mixture. The obtained polymer polyester polyol product has good storage stability and moderate viscosity and a simple process. The polymer polyester polyol is used in the field of polyester system soft foam, soles and other elastomers to achieve significant modification and density reduction effects, greatly improving the load-bearing capacity and dimensional stability of low-density products. At the same time, the use of traditional vinyl monomers is reduced, resulting in greatly improved POP odor. DETAILED DESCRIPTION

[0041] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0042] Example 1

[0043] This embodiment provides a polymer polyester polyol, and the preparation method thereof comprises the following steps:

[0044] In the reactor, the temperature is controlled at 110°C and the pressure is 0.1MPa, and the top material is added dropwise to the bottom material for 3 hours. After the addition is completed, nitrogen is used for pressure protection. After reacting for 1 hour under the pressure of 0.2MPa, the volatile matter is removed by reduced pressure distillation under the pressure of -0.08MPa to obtain a polymer polyester polyol. The bottom material is composed of 431g of polyester polyol (Huafeng product PE-1020) with a molecular weight of 2000g / mol, a functionality of 2, and polymerization monomers of adipic acid and ethylene glycol; the top material is composed of 3.6g of BPO (dibenzoyl peroxide), 300g of styrene, 100g of acrylonitrile, 100g of Japan Daicel FA2D (caprolactone modified acrylate), 1012g of polyester polyol (PE-1020) and 3.3g of dodecyl mercaptan.

[0045] Example 2

[0046] This embodiment provides a polymer polyester polyol, and the preparation method thereof comprises the following steps:

[0047] In the reactor, the temperature is controlled at 110°C and the pressure is 0.1MPa, and the top material is added dropwise to the bottom material for 3 hours. After the addition is completed, nitrogen is used for protection. After reacting for 2 hours under the pressure of 0.2MPa, the volatile matter is removed by reduced pressure distillation under the pressure of -0.08MPa to obtain a polymer polyester polyol. The bottom material is composed of 431g of polyester polyol (Huafeng product PE-1020) with a molecular weight of 2000g / mol, a functionality of 2, and polymerization monomers of adipic acid and ethylene glycol; the top material is composed of 3.6g of BPO (dibenzoyl peroxide), 250g of styrene, 100g of acrylonitrile, 150g of Japan Daicel FA2D (caprolactone modified acrylate), 1012g of polyester polyol (PE-1020) and 3.3g of dodecyl mercaptan.

[0048] Example 3

[0049] This embodiment provides a polymer polyester polyol, and the preparation method thereof comprises the following steps:

[0050] In a reactor, the temperature is controlled at 110°C and the pressure is 0.1 MPa, and the top material is added dropwise to the bottom material for 3 hours. After the addition is completed, nitrogen pressure is used for protection. After reacting for 3 hours under a pressure of 0.2 MPa, volatiles are removed by reduced pressure distillation at a pressure of -0.08 MPa to obtain a polymer polyester polyol; the bottom material is composed of 431 g of a polyester polyol (Huafeng product PE-1020) with a molecular weight of 2000 g / mol, a functionality of 2, and polymerization monomers being adipic acid and ethylene glycol; the top material is composed of 3.6 g of BPO (dibenzoyl peroxide), 250 g of styrene, 50 g of acrylonitrile, 200 g of Japan Daicel FA2D (caprolactone modified acrylate), 1012 g of polyester polyol (PE-1020) and 3.3 g of dodecyl mercaptan.

[0051] Example 4

[0052] This embodiment provides a polymer polyester polyol, and the preparation method thereof comprises the following steps:

[0053] In a reactor, the temperature is controlled at 120° C. and the pressure is 0.1 MPa, and the top material is added dropwise to the bottom material for 3 hours. After the addition is completed, nitrogen pressure is used for protection. After the reaction is carried out at a pressure of 0.2 MPa for 0.5 h, volatiles are removed by reduced pressure distillation at a pressure of -0.08 MPa to obtain a polymer polyester polyol; the bottom material is composed of 334 g of a polyester polyol (Huafeng product PE-1020) with a molecular weight of 2000 g / mol, a functionality of 2, and polymerization monomers being adipic acid and ethylene glycol; the top material is composed of 19.5 g of BPO (dibenzoyl peroxide), 280 g of styrene, 71 g of acrylonitrile, 390 g of Japan Daicel FA2D (caprolactone modified acrylate), 836 g of polyester polyol (PE-1020) and 19.4 g of dodecyl mercaptan.

[0054] Example 5

[0055] This embodiment provides a polymer polyester polyol, and the preparation method thereof comprises the following steps:

[0056] In a reactor, the temperature is controlled at 130° C. and the pressure is 0.1 MPa, and the top material is added dropwise to the bottom material for 3 hours. After the addition is completed, nitrogen pressure is used for protection. After the reaction is carried out at a pressure of 0.2 MPa for 0.3 h, volatiles are removed by reduced pressure distillation at a pressure of -0.08 MPa to obtain a polymer polyester polyol; the bottom material is composed of 496 g of a polyester polyol (Huafeng product PE-1020) with a molecular weight of 2000 g / mol, a functionality of 2, and polymerization monomers being adipic acid and ethylene glycol; the top material is composed of 9.7 g of BPO (dibenzoyl peroxide), 72 g of styrene, 27 g of acrylonitrile, 97 g of FA2D (caprolactone modified acrylate) of Japan Daicel, 1239 g of polyester polyol (PE-1020) and 9.2 g of dodecyl mercaptan.

[0057] Example 6

[0058] This embodiment provides a polymer polyester polyol, and the preparation method thereof comprises the following steps:

[0059] In a reactor, the temperature is controlled at 120°C and the pressure is 0.1 MPa, and the top material is added dropwise to the bottom material for 3 hours. After the addition is completed, nitrogen is used for pressure protection. After the reaction is carried out at a pressure of 0.2 MPa for 1 hour, volatiles are removed by reduced pressure distillation at a pressure of -0.08 MPa to obtain a polymer polyester polyol; the bottom material is composed of 351 g of a polyester polyol (Huafeng product PE-1020) with a molecular weight of 2000 g / mol, a functionality of 2, and polymerization monomers being adipic acid and ethylene glycol; the top material is composed of 19.5 g of BPO (dibenzoyl peroxide), 75 g of styrene, 23 g of acrylonitrile, 585 g of Japan Daicel FA2D (caprolactone modified acrylate), 877 g of polyester polyol (PE-1020) and 19.4 g of dodecyl mercaptan.

[0060] Comparative Example 1

[0061] This comparative example provides a polymer polyester polyol, and its preparation method comprises the following steps:

[0062] In a reactor, the temperature is controlled at 110° C. and the pressure is 0.1 MPa, and the top material is added dropwise to the bottom material. The top material addition time is 3 hours. After the addition is completed, nitrogen pressure is used for protection. After the reaction is carried out under a pressure of 0.2 MPa for 1 hour, volatiles are removed by reduced pressure distillation under a pressure of -0.08 MPa to obtain a polymer polyester polyol; the bottom material is composed of 431 g of a polyester polyol (Huafeng product PE-1020) with a molecular weight of 2000 g / mol, a functionality of 2, and polymerization monomers being adipic acid and ethylene glycol; the top material is composed of 3.6 g of BPO (dibenzoyl peroxide), 400 g of styrene, 100 g of acrylonitrile, 40 g of a dispersant (a dispersant prepared by the method described in Example 1 in patent CN111100251A), 1012 g of polyester polyol (PE-1020) and 3.3 g of dodecyl mercaptan.

[0063] Comparative Example 2

[0064] This comparative example provides a polymer polyester polyol, and its preparation method comprises the following steps:

[0065] In a reactor, the temperature is controlled at 110°C and the pressure is 0.1MPa, and the top material is added dropwise to the bottom material for 3 hours. After the addition is completed, nitrogen pressure is used for protection. After the reaction is carried out at a pressure of 0.2MPa for 1h, volatiles are removed by reduced pressure distillation at a pressure of -0.08MPa to obtain a polymer polyester polyol; the bottom material is composed of 431g of a polyester polyol (Huafeng product PE-1020) with a molecular weight of 2000g / mol, a functionality of 2, and polymerization monomers being adipic acid and ethylene glycol; the top material is composed of 3.6g of BPO (dibenzoyl peroxide), 300g of styrene, 100g of acrylonitrile, 100g of MMA (methyl methacrylate), 1012g of polyester polyol (PE-1020) and 3.3g of dodecyl mercaptan.

[0066] Comparative Example 3

[0067] The Daicel FA2D (caprolactone-modified acrylate) in Example 1 was replaced with an equal amount of poly(ethylene glycol) methacrylate (Mn=526.5, CAS No. 25736-86-1), and the other conditions were the same as in Example 1.

[0068] The appearance, solid content, odor and storage stability of the polymer polyester polyol solutions prepared in the examples and comparative examples are summarized in Table 1. The storage stability refers to the observation of whether stratification occurs after storage at room temperature for 3 months.

[0069] Table 1

[0070]

[0071] Application Examples

[0072] According to the raw material composition in Table 2, the polyurethane elastomer was prepared. The preparation method is as follows:

[0073] All components except isocyanate were put into a container and stirred vigorously, and the temperature was controlled at 50°C to obtain material A. Then, MDI prepolymer (purchased from Shanghai Hongde Polyurethane Co., Ltd., HDISO2128, NCO=26.5%) (material B) was added under the condition of controlling the temperature at 45°C, stirred rapidly, and then the mixture was poured into a closed mold with vents to allow the polyurethane foam to rise and solidify. The polyurethane foam was aged at 60°C for 5 minutes and then taken out. The prepared polyurethane microcellular elastomer was aged at room temperature for 24 hours and then the performance was tested. The results are shown in Table 2.

[0074] The performance test method is as follows:

[0075] (1) Foam density: tested according to the method of GB / T 6343-2009;

[0076] (2) Tensile strength: tested according to the method of GB / T 6344-2008;

[0077] (3) Elongation at break: tested according to the method of GB / T 6344-2008;

[0078] (4) Hardness: Tested according to the method of GB / T 10807-89.

[0079] Table 2

[0080]

[0081]

[0082] Table 3

[0083]

[0084]

[0085] It can be seen that the polymer polyester polyol prepared by the present invention can have better control over the polymer particles in the polymer polyester polyol even without adding a dispersant, and has extremely low odor. Application in microporous elastomers can reduce product density and increase hardness.

[0086] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the polymer polyester polyol and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A polymer polyester polyol, characterized in that The raw materials for preparing the polymer polyester polyol include the following components in percentage by weight:

2. The polymer polyester polyol according to claim 1, characterized in that The number average molecular weight of the polyester polyol is 1000-4000 g / mol; Preferably, the acid value of the polyester polyol is less than 3 mgKOH / g; Preferably, the polyester polyol has a viscosity of 1500-6000 mPa.s at 40°C; Preferably, the polyester polyol is prepared by polycondensation of a diol and a dicarboxylic acid or anhydride; Preferably, the diol is selected from any one or a combination of at least two of ethylene glycol, diethylene glycol, 1,4-butanediol or 2-methyl-1,3-propanediol; Preferably, the dicarboxylic acid is selected from any one of adipic acid, oxalic acid, succinic acid, glutaric acid or azelaic acid, or a combination of at least two thereof; Preferably, the acid anhydride is selected from any one of succinic anhydride, adipic anhydride, azelaic anhydride, isophthalic anhydride, phthalic anhydride or hexahydrobiphenyl, or a combination of at least two thereof.

3. The polymer polyester polyol according to claim 1 or 2, characterized in that The polyester modified acrylic monomer is selected from one or a combination of at least two of caprolactone modified (meth) acrylate, caprolactone modified hydroxyethyl methacrylate, caprolactone modified hydroxypropyl acrylate or caprolactone modified hydroxypropyl methacrylate.

4. The polymer polyester polyol according to any one of claims 1 to 3, characterized in that The other vinyl-containing monomers are selected from one or a combination of at least two of styrene, acrylonitrile, butadiene, methyl styrene, ethyl styrene, acrylic acid, acrylic acid ester or methyl methacrylate.

5. The polymer polyester polyol according to any one of claims 1 to 4, characterized in that The initiator is selected from one or a combination of at least two of benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, tert-amyl peroxide 2-ethylhexyl acid ester, tert-butyl peroxide 2-ethylhexyl acid ester, 1,1'-bis(tert-amyl peroxy)cyclohexane, 1,1'-bis(tert-butyl peroxy)-3,3,5-trimethylcyclohexane, tert-amyl peroxyacetate, tert-amyl peroxybenzoate, tert-butyl peroxy 3,5,5'trimethylhexanoate or tert-butyl peroxybenzoate; Preferably, the chain transfer agent is selected from mercaptan compounds; Preferably, the thiol compound is selected from one or a combination of at least two of isopropyl alcohol, dodecyl mercaptan, isopentyl mercaptan or hexadecanethiol.

6. The method for preparing a polymer polyester polyol according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: Adding material A to material B for reaction to obtain the polymer polyester polyol; The material A contains polyester-modified acrylic monomers, other monomers containing vinyl groups, an initiator and polyester polyols, and the material B is polyester polyols.

7. The preparation method according to claim 6, characterized in that: The mass ratio of the polyester polyol in material A to the polyester polyol in material B is 1:1-3:1; Preferably, the material A is added to the material B by dropwise addition; Preferably, material A is added dropwise to material B within 1.5-3 hours.

8. The preparation method according to claim 6 or 7, characterized in that: The reaction temperature is 110°C-130°C, and the reaction time is 0.3-3h; Preferably, the reaction is carried out under nitrogen protection; Preferably, the reaction is carried out at a pressure of 0.20-0.4 MPa.

9. A polyurethane, characterized in that The polyurethane is prepared from the polymer polyester polyol and isocyanate as described in any one of claims 1 to 5.

10. Use of the polymer polyester polyol according to any one of claims 1 to 5 or the polyurethane according to claim 9 in the preparation of polyurethane elastomer products; Preferably, the polyurethane elastomer product includes a polyurethane sole or a polyurethane soft foam.

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