PPDI-based shoe sole stock solution, and preparation method and application thereof

Abstract

The application discloses a PPDI-based shoe sole stock solution and a preparation method and application thereof. The PPDI-based shoe sole stock solution comprises A component, B component and C component. The preparation method of the B component comprises the following steps: after oligomer dihydric alcohol 1 is dehydrated, the oligomer dihydric alcohol 1 is fully reacted with PPDI under the protection of an inert atmosphere at 50-70 DEG C, wherein the PPDI is added in excess of 1-10% of the theoretical complete reaction with the oligomer dihydric alcohol 1, then the temperature is increased to 70-90 DEG C, a trimerization catalyst is added and the reaction is continued for 1-2 hours, then a polymerization inhibitor is added to deactivate the trimerization catalyst, and the B component is obtained; the raw material composition of the A component comprises oligomer dihydric alcohol 2, a foam stabilizer and water and an optional chain extender; the raw material composition of the C component comprises a catalyst. Through the specific process, the content of free PPDI monomers in the B component of the shoe sole stock solution is limited, and the self-polymerization reaction of free PPDI is rapidly completed in a short time, and the stability of the B component is improved.

Description

Technical Field

[0001] This invention relates to the field of polyurethane shoe sole raw materials, specifically to a PPDI-based shoe sole raw material, its preparation method, and its application. Background Technology

[0002] Sole base material is the raw material for making shoe soles. Shoe soles made from polyurethane sole base material are lightweight, high-strength, tough, and wear-resistant, and have a large market capacity.

[0003] Currently, the majority of polyurethane shoe sole raw materials, specifically component B, are obtained by reacting diphenylmethane diisocyanate (MDI) with polyester polyols. Due to the molecular structure characteristics of MDI, the rebound and compression deformation properties of shoe sole materials prepared from it cannot be further improved.

[0004] In addition, existing technologies also disclose the use of other isocyanates to prepare component B.

[0005] For example, patent specification CN118240167A discloses a polyether-type polyurethane elastomer applicable to shoe outsoles and its preparation method. This polyurethane elastomer is obtained by reacting an isocyanate reactive component (Component A) and an isocyanate component (Component B). Component B is selected from isocyanate monomers, isocyanate prepolymers, and isocyanate derivatives. The isocyanate monomers include diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), and hexamethylenetetramine. One or more of the following: hydroxyl diisocyanate (HDI), naphthalene diisocyanate (NDI), terephthalic diisocyanate (PPDI), 1,4-cyclohexane diisocyanate (CHDI), phenylenediamine diisocyanate (XDI), and cyclohexanedimethyl diisocyanate (HXDI); isocyanate derivatives including one or more of the following: carbodiimide-modified 4,4'-MDI, TDI dimer, TDI trimer, HDI dimer, HDI trimer, and TDI-TMP adduct; isocyanate prepolymers are obtained by reacting polyether polyols with isocyanate monomers.

[0006] Prior to this application, the applicant also disclosed a fast-release HDI-based shoe sole raw material and its preparation method, see the patent specification with publication number CN118063738A. The HDI-based polyurethane shoe sole raw material of this patent technology uses an aliphatic isocyanate component that is resistant to yellowing, thereby improving the yellowing resistance of the product. It also uses a composite catalytic system to improve the catalytic efficiency of the catalyst.

[0007] Currently, in order to improve the rebound and compression set properties of shoe sole raw materials, the applicant focuses on PPDI-based shoe sole raw materials. During the research process, the applicant found that PPDI is highly reactive, easily self-polymerizes, and easily sublimates at high temperatures, making it difficult to use in the synthesis of component B of shoe sole raw materials. Furthermore, free PPDI monomers can affect the stability of shoe sole raw materials.

[0008] However, the current method for preparing low-free PPDI prepolymer mainly involves solvent dissolution followed by thin-film evaporation. This method is complex and can cause pipe blockage during evaporation, limiting its application in the field of shoe sole raw materials. Summary of the Invention

[0009] Based on the above-mentioned realities, this invention provides a PPDI-based shoe sole raw material, its preparation method, and its applications. Due to the unique symmetrical and regular molecular structure of terephthalic diisocyanate (PPDI), the polyurethane synthesized from PPDI has greater cohesive energy and a higher degree of phase separation. In the existing fields of castable and thermoplastic polyurethane elastomers, the use of PPDI has achieved superior resilience, compression set, abrasion resistance, and mechanical properties of polyurethane.

[0010] [1] A PPDI-based shoe sole raw material, comprising component A, component B and component C;

[0011] The preparation method of component B includes: dehydrating oligomeric diol 1 and reacting it with PPDI under an inert atmosphere at 50-70°C (e.g., 60°C), wherein PPDI is added in excess of 1%-10% based on the theoretical complete reaction with oligomeric diol 1, then the temperature is raised to 70-90°C (e.g., 80°C) and a trimerizing catalyst is added to continue the reaction for 1-2 hours (e.g., 1.5 hours), followed by the addition of a polymerization inhibitor to deactivate the trimerizing catalyst, thereby obtaining component B;

[0012] The raw material composition of component A includes oligomeric diol 2, foam stabilizer, water, and a chain extender that can be added (either added or not).

[0013] The raw material composition of component C includes a catalyst.

[0014] In the PPDI-based shoe sole raw material of this invention, component B is prepared by reacting terephthalic diisocyanate (PPDI) with oligomeric diol 1, and by the self-polymerization reaction of free PPDI. This invention uses PPDI instead of traditional MDI to synthesize shoe sole raw materials. Due to the symmetrical and regular molecular structure of PPDI, it can form denser hard segment microdomains within the product and produce a high degree of microphase separation, resulting in shoe materials prepared from PPDI-based shoe sole raw materials exhibiting superior rebound and compression resistance. Furthermore, this invention, by limiting the content of free PPDI during the preparation of component B of the shoe sole raw material, while simultaneously promoting the self-polymerization reaction of free PPDI, prepares a stable PPDI-based shoe sole raw material component B. The trimer generated by the self-polymerization of PPDI can provide a certain cross-linking structure during the shoe material production process, shortening the demolding time and improving the strength of the shoe sole.

[0015] The applicant's research found that when PPDI is used to react with polyols to prepare component B, even if PPDI and polyol are added according to the stoichiometric ratio, in practice, phenomena such as PPDI self-polymerization cannot guarantee that all polyols will react. This means that unreacted polyols will remain in the final component B, which is undesirable and detrimental to the performance of the final shoe sole product. Therefore, this invention adds PPDI in an excess of 1%-10% to ensure a theoretically complete reaction with oligomeric diol 1, thereby maximizing the complete reaction of oligomeric diol 1.

[0016] In fact, the applicant's research found that due to the high reactivity of PPDI, self-polymerization of PPDI inevitably occurs when it reacts with polyols to prepare component B. Furthermore, because an excessive amount of PPDI needs to be added during the initial feeding to ensure complete reaction of the polyol (the reason for this addition has been explained above), residual free PPDI monomers remain in component B after the reaction. These free PPDI monomers continue to self-polymerize within component B, resulting in varying degrees of self-polymerization of free PPDI monomers depending on storage time. This leads to unstable viscosity of component B, changing with storage time, and consequently, inconsistent quality and performance of the resulting shoe sole products. Even from the same batch of stock solution, the quality and performance of the shoe sole products produced vary depending on the production time. This does not meet the company's requirements for stable production. Moreover, if component B is stored for too long, the degree of self-polymerization of free PPDI monomers in component B becomes too high, resulting in excessive cross-linking, which will actually reduce the quality and performance of the final shoe sole product. This is an outcome the company is even more unwilling to accept.

[0017] Therefore, the applicant proposes the PPDI-based shoe sole raw material of this invention, which strictly limits the preparation method of component B, requiring that PPDI be added in excess of only 1%-10%, and not more, otherwise the excessive free PPDI monomers will be difficult to handle. Based on this, the following technical route is proposed: After the oligomeric diol 1 reacts fully with PPDI, a trimerizing catalyst is added to rapidly self-polymerize the remaining free PPDI monomers to a reasonable level that is conducive to improving the quality and performance of the final shoe sole product, that is, to accelerate the self-polymerization in advance. Then, a polymerization inhibitor is added to deactivate the trimerizing catalyst and inhibit the subsequent self-polymerization process. This not only improves the production efficiency of component B, but also keeps the viscosity of the obtained component B stable over a long period of time, extending the shelf life of component B in actual production. This allows the company to plan production tasks more flexibly, ensuring the quality and performance stability of shoe sole products. At the same time, it can also significantly improve the quality and performance of shoe sole products.

[0018] In summary, this invention limits the content of free PPDI monomers in component B of the sole stock solution through a specific process, while rapidly completing the self-polymerization reaction of free PPDI in a short time, thereby improving the stability of component B, further optimizing the composition of the sole stock solution formulation, and preparing a PPDI-based sole stock solution with excellent rebound, compression deformation, and tear resistance.

[0019] In this invention, the inert atmosphere refers to a gaseous atmosphere that does not participate in the reaction, such as one or a combination of rare gas atmospheres, nitrogen atmospheres, etc.

[0020] In the preparation method of component B, the dehydration process of oligomeric diol 1 may include: removing water from oligomeric diol 1 at a temperature of 100-120°C and a vacuum degree of 0.08-0.1 MPa. Further, the dehydration time may be 1-2 hours.

[0021] In the preparation method of component B, the reaction time of the dehydrated oligomeric diol 1 with PPDI at 50-70°C under an inert atmosphere can be 1-3 hours, for example 2 hours.

[0022] In the preparation method of component B, the number average molecular weight of the oligomeric diol 1 can be 800-1500 g / mol, such as 1000 g / mol, 1200 g / mol, etc.

[0023] In the preparation method of component B, the oligomeric diol 1 may include at least one of polytetrahydrofuran ether diol, polypropylene glycol, and polyester diol. Further, the polyester diol may include at least one of the grades P1110, P1215, and P1309 from Meirui New Materials Co., Ltd.

[0024] In the preparation method of component B, the trimerizing catalyst may include one or more of 2-hydroxy-N,N,N-trimethyl-1-propylcarbamate (TMR-2), potassium 2-ethylhexanoate (K15), ammonium 2-hydroxypropyltrimethylisooctanoate (TMR), and tributylphosphine (TBP).

[0025] In the preparation method of component B, the amount of the trimerizing catalyst can be 50-200 ppm of the total mass of component B.

[0026] In the preparation method of component B, the polymerization inhibitor may include at least one of di(2-ethylhexyl) phosphate and dibutyl phosphate.

[0027] In the preparation method of component B, the amount of the polymerization inhibitor can be 1.05-1.2 times the mass of the trimerizing catalyst added.

[0028] In the preparation method of component B, after adding the polymerization inhibitor, the mixture is stirred for 0.5-1 hour (e.g., 0.7 hours) to obtain component B.

[0029] In the raw material composition of component A, the mass ratio of oligomeric polyol 2, chain extender, water, and foam stabilizer can be 100:0-10:0.5-2.5:0.5-2.

[0030] In the raw material composition of component A, the number average molecular weight of the oligomer diol 2 can be 1500-4000 g / mol, for example 1800 g / mol, 2000 g / mol, 3000 g / mol, etc.

[0031] In the raw material composition of component A, the oligomer diol 2 may include at least one of polytetrahydrofuran ether diol and polyester diol. Further, the polyester diol may include at least one of the grades P1320, P1330, P1340, P1220, P1230, and P1240 from Meirui New Materials Co., Ltd.

[0032] In the raw material composition of component A, the chain extender may include one or more of 1,4-butanediol (BDO), 2-methyl-1,3-propanediol (MPO), and ethylene glycol (EG).

[0033] In the raw material composition of component A, the amount of water can be 0.5%-2.5% of the mass of the oligomeric diol 2, for example, 1.5%, 1.8%, 2%, etc. In the PPDI-based shoe sole raw material system of the present invention, water can act as a foaming agent.

[0034] In the raw material composition of component A, the foam stabilizer can be a conventionally selected one in the art, such as a polysiloxane foam stabilizer.

[0035] In some embodiments, the preparation method of component A may include: mixing oligomeric diol 2, foam stabilizer, water, and optionally added chain extender at 50-70°C to obtain component A.

[0036] In the raw material composition of component C, the catalyst may include an organometallic catalyst and an amine catalyst. Further, the mass ratio of the organometallic catalyst to the amine catalyst may be 100:20-100, for example, 100:30, 100:50, 100:80, etc.

[0037] In the raw material composition of component C, the organometallic catalyst may include at least one of dibutyltin dilaurate (T-12), stannous octoate (T-9), di(dodecyl sulfide)dibutyltin (T-120), zinc isooctanoate, and bismuth isooctanoate.

[0038] In the raw material composition of component C, the amine catalyst may include at least one of triethylenediamine (A33), tetramethyldiethylenetriamine, N,N-dimethyldiethanolamine (DMAEE), bismorpholinodiethyl ether (DMDEE), and bis(dimethylaminoethyl) ether (A1).

[0039] The mass ratio of component A to component C in the PPDI-based shoe sole stock solution can be 100:0.3-1, for example, 100:0.5, 100:0.8, etc.

[0040] The mass ratio of component A to component B in the PPDI-based shoe sole stock solution can be 100:110-250, for example, 100:113, 100:160, 100:170, 100:178, 100:200, 100:210, 100:239, etc.

[0041] [2] The preparation method of the PPDI-based shoe sole raw material according to [1] includes:

[0042] Mix oligomeric diol 2, foam stabilizer, water, and optionally chain extender at 50-70°C to obtain component A;

[0043] After dehydration of oligomeric diol 1, it is reacted with PPDI at 50-70°C under an inert atmosphere. PPDI is added in excess of 1%-10% based on the theoretical complete reaction with oligomeric diol 1. Then, the temperature is raised to 70-90°C, a trimerizing catalyst is added, and the reaction continues for 1-2 hours. Next, a polymerization inhibitor is added to deactivate the trimerizing catalyst, resulting in component B.

[0044] Component A and component C are mixed evenly, and then mixed with component B to obtain the PPDI-based shoe sole stock solution.

[0045] [3] Application of PPDI-based shoe sole stock solution as described in [1] in the preparation of shoe soles.

[0046] [4] A polyurethane microporous elastomer is obtained by foaming materials including the PPDI-based shoe sole raw material described in [1].

[0047] [5] A method for preparing a polyurethane microporous elastomer includes: foaming the PPDI-based shoe sole raw material described in [1] to obtain the polyurethane microporous elastomer.

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

[0049] 1. Using PPDI instead of traditional MDI synthetic shoe sole raw material results in the formation of denser hard segment micro-regions and a high degree of microphase separation within the product due to the symmetrical and regular molecular structure of PPDI. This leads to shoe materials made from PPDI-based shoe sole raw material having superior rebound and compression resistance properties.

[0050] 2. By limiting the content of free PPDI and promoting the self-polymerization reaction of free PPDI during the preparation of component B of the shoe sole raw material, a stable PPDI-based shoe sole raw material component B was prepared. At the same time, the trimer generated by the self-polymerization of PPDI can provide a certain cross-linking structure during the shoe material production process, shortening the demolding time and improving the strength of the shoe sole. Detailed Implementation

[0051] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Operating methods not specifically specified in the following embodiments are generally performed under conventional conditions or as recommended by the manufacturer.

[0052] Unless otherwise specified, the molecular weight units in the following examples are all g / mol, the molecular weights of the polymers are all exponential molecular weights, and the foam stabilizers are all commercially available polysiloxane foam stabilizers.

[0053] Example 1:

[0054] (1) Preparation of component B: 500g of polytetrahydrofuran ether diol with a molecular weight of 1000 was stirred for 1-2h at a temperature of 100-120℃ and a vacuum of 0.08-0.1MPa to remove water. Then, the temperature was lowered to 50℃ and 176g of PPDI was added. The mixture was stirred for 3h under nitrogen protection. Then, the temperature was raised to 70℃ and 0.07g of trimerizing catalyst TMR-2 was added. The reaction was continued for 2h. Then, 0.08g of polymerization inhibitor dibutyl phosphate was added and stirred for 1h before discharging to obtain component B.

[0055] (2) Preparation of component A: 100g of polytetrahydrofuran ether diol with a molecular weight of 1800, 1g of foaming agent and 1.5g of water are mixed at 50-70℃ to obtain component A.

[0056] (3) Preparation of component C: T-12 and A33 were mixed evenly in a mass ratio of 100:50 to obtain component C.

[0057] Mix component A and component C at a mass ratio of 100:0.5 until homogeneous, then mix them with component B at a mass ratio of 100:140 and inject the mixture into a mold. Foaming will produce polyurethane microporous elastomer.

[0058] Example 2:

[0059] (1) Preparation of component B: 300g of P1110 with a molecular weight of 1000 and 200g of polypropylene glycol with a molecular weight of 1000 were stirred for 1-2h at a temperature of 100-120℃ and a vacuum degree of 0.08-0.1MPa to remove water. Then, the temperature was lowered to 60℃ and 170g of PPDI was added. The mixture was stirred and reacted for 2h under nitrogen protection. Then, the temperature was raised to 80℃ and 0.05g of trimerizing catalyst K15 was added. The reaction was continued for 1.5h. Then, 0.06g of polymerization inhibitor dibutyl phosphate was added and stirred for 0.7h before discharging to obtain component B.

[0060] (2) Preparation of component A: 100g of P1320 with a molecular weight of 2000, 3g of BDO, 1g of foaming agent and 2g of water were mixed at 50-70℃ to obtain component A.

[0061] (3) Preparation of component C: T-120 and A1 were mixed evenly at a mass ratio of 100:30 to obtain component C.

[0062] Mix component A and component C at a mass ratio of 100:0.8 until homogeneous, then mix them with component B at a mass ratio of 100:200 and inject the mixture into a mold. Foaming will produce polyurethane microporous elastomer.

[0063] Example 3:

[0064] (1) Preparation of component B: 500g of P1309 with a molecular weight of 900 was stirred for 1-2h at a temperature of 100-120℃ and a vacuum degree of 0.08-0.1MPa to remove water. Then, the temperature was lowered to 70℃ and 190g of PPDI was added. The mixture was stirred for 1h under nitrogen protection. Then, the temperature was raised to 90℃ and 0.1g of trimerizing catalyst TBP was added. The reaction was continued for 1h. Then, 0.11g of polymerization inhibitor di(2-ethylhexyl) phosphate was added and stirred for 0.5h before discharging to obtain component B.

[0065] (2) Preparation of component A: 100g of P1220 with a molecular weight of 2000, 3g of BDO, 1g of foaming agent and 1.8g of water were mixed at 50-70℃ to obtain component A.

[0066] (3) Preparation of component C: Bismuth isooctanoate and DMDEE were mixed evenly at a mass ratio of 100:80 to obtain component C.

[0067] Mix component A and component C at a mass ratio of 100:0.3 until homogeneous, then mix them with component B at a mass ratio of 100:170 and inject the mixture into a mold. Foaming will produce polyurethane microporous elastomer.

[0068] Example 4:

[0069] (1) Preparation of component B: 500g of P1215 with a molecular weight of 1500 was stirred for 1-2h at a temperature of 100-120℃ and a vacuum of 0.08-0.1MPa to remove water. Then, the temperature was lowered to 50℃ and 115g of PPDI was added. The mixture was stirred for 2h under nitrogen protection. Then, the temperature was raised to 70℃ and 0.07g of trimerizing catalyst TMR-2 was added. The reaction was continued for 2h. Then, 0.08g of polymerization inhibitor dibutyl phosphate was added and stirred for 1h before discharging to obtain component B.

[0070] (2) Preparation of component A: 100g of P1330 with a molecular weight of 3000, 3g of MPO, 1g of foaming agent and 1.5g of water were mixed at 50-70℃ to obtain component A.

[0071] (3) Preparation of component C: T-9 and DMAEE were mixed evenly at a mass ratio of 100:50 to obtain component C.

[0072] Mix component A and component C at a mass ratio of 100:0.8 until homogeneous, then mix them with component B at a mass ratio of 100:210 and inject the mixture into a mold. Foaming will produce polyurethane microporous elastomer.

[0073] Example 5:

[0074] (1) Preparation of component B: 500g of polytetrahydrofuran ether diol with a molecular weight of 1000 was stirred for 1-2h at a temperature of 100-120℃ and a vacuum of 0.08-0.1MPa to remove water. Then, the temperature was lowered to 60℃ and 176g of PPDI was added. The mixture was stirred for 2h under nitrogen protection. Then, the temperature was raised to 80℃ and 0.07g of trimerizing catalyst TMR was added. The reaction was continued for 1.5h. Then, 0.08g of polymerization inhibitor dibutyl phosphate was added and stirred for 0.7h before discharging to obtain component B.

[0075] (2) Preparation of component A: 100g of P1220 with a molecular weight of 2000, 5g of EG, 1g of foaming agent and 1g of water are mixed at 50-70℃ to obtain component A.

[0076] (3) Preparation of component C: T-12 and A33 were mixed evenly in a mass ratio of 100:50 to obtain component C.

[0077] Mix component A and component C at a mass ratio of 100:1 until homogeneous, then mix them with component B at a mass ratio of 100:170 (component A to component B) and inject the mixture into a mold. Foaming will produce polyurethane microporous elastomer.

[0078] Comparative Example 1: The method of Comparative Example 1 is basically the same as that of Example 1, except that the amount of PPDI added is 184g, at which point the theoretical free amount of PPDI is 15%.

[0079] Comparative Example 2: The method of Comparative Example 2 is basically the same as that of Example 1, except that the amount of PPDI added is 160g, at which point the theoretical free amount of PPDI is 0%.

[0080] Comparative Example 3: The method for Comparative Example 3 is basically the same as that for Example 1, except for the preparation of component B: 500g of polytetrahydrofuran ether diol with a molecular weight of 1000 was stirred for 1-2 hours at a temperature of 100-120℃ and a vacuum degree of 0.08-0.1MPa to remove water. Then, the temperature was lowered to 50℃, and 176g of PPDI was added. The mixture was stirred and reacted for 3 hours under nitrogen protection to obtain component B. Component B was immediately used to prepare polyurethane microporous elastomer. Experiments showed that the viscosity of component B in Comparative Example 3 increased significantly after a period of time, and solidified into a gel after 30 days.

[0081] Table 1 shows the performance test results of the microporous elastomers prepared in each embodiment and comparative example.

[0082] Table 1

[0083]

[0084] Compared with Example 1, Comparative Example 1 showed worse tear strength and compressive deformation properties, indicating that excessive PPDI (>10%) has an adverse effect on microporous elastomers.

[0085] Compared with Example 1, Example 1 showed better tear strength, compression set and resilience, indicating that an appropriate excess of PPDI (1%-10%) is beneficial to improving the performance of microporous elastomers.

[0086] Compared with Example 1, the viscosity of component B in Comparative Example 3 increased and even gelled after a long period of storage, indicating that the addition of the trimer catalyst and polymerization inhibitor of the present invention can greatly improve the stability of the shoe sole raw material.

[0087] Furthermore, it should be understood that after reading the above description of the present invention, those skilled in the art can make various alterations or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A PPDI-based shoe sole concentrate, characterized in that, Includes components A, B, and C; The preparation method of component B includes: dehydrating oligomeric diol 1 and reacting it with PPDI under an inert atmosphere at 50-70°C, wherein PPDI is added in excess of 1%-10% based on the theoretical complete reaction with oligomeric diol 1, then heating to 70-90°C and adding a trimerizing catalyst to continue the reaction for 1-2 hours, followed by adding a polymerization inhibitor to deactivate the trimerizing catalyst, thus obtaining component B; The raw material composition of component A includes oligomeric diol 2, foam stabilizer, water, and optional chain extender; The raw material composition of component C includes a catalyst.

2. The PPDI-based shoe sole raw material according to claim 1, characterized in that, In the preparation method of component B: The dehydration process of oligomeric diol 1 includes: removing water from oligomeric diol 1 at a temperature of 100-120℃ and a vacuum degree of 0.08-0.1MPa; the dehydration time is 1-2 hours; After dehydration, oligomeric diol 1 reacts with PPDI at 50-70°C for 1-3 hours under an inert atmosphere. The number-average molecular weight of the oligomeric diol 1 is 800-1500 g / mol; The oligomeric diol 1 includes at least one of polytetrahydrofuran ether diol, polypropylene glycol, and polyester diol, wherein the polyester diol includes at least one of the grades P1110, P1215, and P1309 of Meirui New Materials Co., Ltd. The trimerizing catalyst includes one or more of 2-hydroxy-N,N,N-trimethyl-1-propylcarbamate, potassium 2-ethylhexanoate, ammonium 2-hydroxypropyltrimethylisooctanoate, and tributylphosphine. The amount of the trimerizing catalyst used is 50-200 ppm of the total mass of component B; The polymerization inhibitor includes at least one of di(2-ethylhexyl) phosphate and dibutyl phosphate; The amount of the polymerization inhibitor is 1.05-1.2 times the mass of the trimerizing catalyst added; After adding the polymerization inhibitor, stir for 0.5-1 hour to obtain component B.

3. The PPDI-based shoe sole raw material according to claim 1, characterized in that, The raw material composition of component A includes: The mass ratio of oligomeric polyol 2, chain extender, water, and foam stabilizer is 100:0-10:0.5-2.5:0.5-2; The number-average molecular weight of the oligomeric diol 2 is 1500-4000 g / mol; The oligomer diol 2 includes at least one of polytetrahydrofuran ether diol and polyester diol, wherein the polyester diol includes at least one of the grades P1320, P1330, P1340, P1220, P1230, and P1240 of Meirui New Materials Co., Ltd. The chain extender includes one or more of 1,4-butanediol, 2-methyl-1,3-propanediol, and ethylene glycol; The foam leveling agent includes polysiloxane-based foam leveling agents.

4. The PPDI-based shoe sole raw material according to claim 1 or 3, characterized in that, The preparation method of component A includes: mixing oligomeric diol 2, foam stabilizer, water, and optionally added chain extender at 50-70℃ to obtain component A.

5. The PPDI-based shoe sole raw material according to claim 1, characterized in that, The raw material composition of component C is as follows: The catalysts include organometallic catalysts and amine catalysts; The mass ratio of the organometallic catalyst to the amine catalyst is 100:20-100; The organometallic catalyst includes at least one of dibutyltin dilaurate, stannous octanoate, di(dodecyl sulfide)dibutyltin, zinc isooctanoate, and bismuth isooctanoate. The amine catalyst includes at least one of triethylenediamine, tetramethyldiethylenetriamine, N,N-dimethyldiethanolamine, bismorpholinodiethyl ether, and bis(dimethylaminoethyl) ether.

6. The PPDI-based shoe sole raw material according to claim 1, characterized in that, The mass ratio of component A to component C is 100:0.3-1; The mass ratio of component A to component B is 100:110-250.

7. The method for preparing PPDI-based shoe sole stock solution according to any one of claims 1-6, characterized in that, include: Mix oligomeric diol 2, foam stabilizer, water, and optionally chain extender at 50-70°C to obtain component A; After dehydration of oligomeric diol 1, it is reacted with PPDI at 50-70°C under an inert atmosphere. PPDI is added in excess of 1%-10% based on the theoretical complete reaction with oligomeric diol 1. Then, the temperature is raised to 70-90°C, a trimerizing catalyst is added, and the reaction continues for 1-2 hours. Next, a polymerization inhibitor is added to deactivate the trimerizing catalyst, resulting in component B. Component A and component C are mixed evenly, and then mixed with component B to obtain the PPDI-based shoe sole stock solution.

8. The application of the PPDI-based shoe sole stock solution according to any one of claims 1-6 in the preparation of shoe soles.

9. A polyurethane microporous elastomer, characterized in that, It is prepared by foaming materials including the PPDI-based shoe sole raw material as described in any one of claims 1-6.

10. A method for preparing a polyurethane microporous elastomer, characterized in that, include: The polyurethane microporous elastomer is prepared by foaming the PPDI-based shoe sole raw material according to any one of claims 1-6.

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