PPDI-based sole stock solution as well as preparation method and application thereof

Abstract

The invention discloses a PPDI-based sole stock solution as well as a preparation method and application thereof. The PPDI-based sole stock solution comprises a component A, a component B and a component C, a preparation method of the component B comprises the following steps: dehydrating oligomer dihydric alcohol 1, fully reacting with PPDI at 50-70 DEG C under inert atmosphere protection, adding PPDI according to 1-10% excess of theoretical complete reaction between PPDI and oligomer dihydric alcohol 1, heating to 70-90 DEG C, adding a trimerization catalyst, continuously reacting for 1-2 hours, and adding a polymerization inhibitor to deactivate the trimerization catalyst to obtain the component B; the component A comprises the following raw materials: oligomer dihydric alcohol 2, a foam stabilizer, water and a selectively added chain extender; the component C is prepared from a catalyst. Through a specific process, the content of PPDI free monomers in the component B of the sole stock solution is limited, meanwhile, the self-polymerization reaction of the free PPDI is rapidly completed within a short time, and the stability of the component B is improved.

Description

Technical Field

[0001] The invention relates to the field of polyurethane sole stock solution, and in particular to a PPDI-based sole stock solution and a preparation method and application thereof. Background Art

[0002] The sole stock solution is the raw material for preparing the soles. The soles prepared from the polyurethane sole stock solution have the characteristics of light weight, high strength, good toughness, wear resistance, etc., and have a large market capacity.

[0003] At present, most of the B component of polyurethane sole stock solution is obtained by reacting diphenylmethane diisocyanate (MDI) with polyester polyol. Due to the molecular structure characteristics of diphenylmethane diisocyanate (MDI), the rebound and compression deformation properties of the sole material prepared from it cannot be further improved.

[0004] In addition, there are also prior arts that disclose that other isocyanates can be used to prepare the B component.

[0005] For example, the patent specification with publication number CN118240167A discloses a polyether polyurethane elastomer applicable to shoe outsoles and a preparation method thereof, wherein the polyurethane elastomer is obtained by reacting an isocyanate reactive component (component A) with an isocyanate component (component B), wherein component B is selected from isocyanate monomers, isocyanate prepolymers, and isocyanate derivatives, and the isocyanate monomers include diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (IPDI), and isocyanate derivatives. The isocyanate derivatives include one or more of carbodiimide-modified 4,4'-MDI, TDI dimer, TDI trimer, HDI dimer, HDI trimer, and TDI-TMP adducts; and the isocyanate prepolymer is obtained by reacting a polyether polyol with an isocyanate monomer.

[0006] Before filing the present application, the applicant also disclosed a quick-demolding HDI-based sole stock solution and a preparation method thereof, see the patent specification with publication number CN118063738A. The HDI-based polyurethane sole stock solution of the patented technology adopts a yellowing-resistant aliphatic isocyanate component to improve the yellowing resistance of the product, and adopts a composite catalytic system to improve the catalytic efficiency of the catalyst.

[0007] Nowadays, in order to improve the rebound and compression properties of sole stock solutions, the applicant focuses on PPDI-based sole stock solutions. During the research process, the applicant found that PPDI is highly active and easy to self-polymerize and sublimate at high temperatures, making it difficult to synthesize the B component of the sole stock solution, and the free PPDI monomer will affect the stability of the sole stock solution.

[0008] However, the current method for preparing low-free PPDI prepolymers is mainly to dissolve them in solvents and then process them using a thin film evaporator. This method has complex process operations and there is also the problem of pipeline clogging during evaporation, which limits its application in the field of shoe sole concentrates. Summary of the invention

[0009] Based on the above reality, the present invention provides a PPDI-based sole stock solution and its preparation method and application. Due to the unique symmetrical and regular molecular structure of p-phenylene diisocyanate (PPDI), the polyurethane molecules synthesized by PPDI have greater cohesive energy and a high degree of phase separation. In the existing field of cast and thermoplastic polyurethane elastomers, the use of PPDI achieves better rebound, compression deformation, wear resistance and mechanical properties of polyurethane.

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

[0011] The preparation method of component B comprises: dehydrating oligomer diol 1 and reacting it with PPDI at 50-70° C. (e.g., 60° C.) under inert atmosphere protection, wherein PPDI is added in excess of 1%-10% according to theoretical complete reaction with oligomer diol 1, then heating to 70-90° C. (e.g., 80° C.), adding a trimerization catalyst, and continuing the reaction for 1-2 hours (e.g., 1.5 hours), and then adding an inhibitor to deactivate the trimerization catalyst to obtain component B;

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

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

[0014] In the PPDI-based sole stock solution of the present invention, component B is prepared by the reaction of p-phenylene diisocyanate (PPDI) with oligomer diol 1, and the self-polymerization reaction of free PPDI. The present invention uses PPDI to replace the traditional MDI to synthesize the sole stock solution. Due to the symmetrical and regular molecular structure of PPDI, a more compact hard segment micro-region can be formed in the product, and a high degree of micro-phase separation is generated, so that the shoe material prepared by the PPDI-based sole stock solution has more excellent rebound, compression resistance and other properties. Further, the present invention limits the free PPDI content in the preparation process of the sole stock solution component B, and promotes the self-polymerization reaction of free PPDI, so as to prepare a stable PPDI-based sole stock solution component B, and the trimer produced by the self-polymerization of PPDI can provide a certain cross-linking structure in the shoe material production process, shorten the demolding time and improve the sole strength.

[0015] The applicant has found that when PPDI is used to react with polyols to prepare component B, if PPDI and polyols are added according to the chemical reaction stoichiometric ratio, the polyols cannot be fully reacted in actual operation due to the existence of phenomena such as PPDI self-polymerization, that is, unreacted polyols will still remain in the final component B, which is undesirable and is not conducive to the performance of the final sole product. Based on this, the present invention adds PPDI in excess of 1%-10% according to the theoretical complete reaction with oligomer diol 1, so that oligomer diol 1 can be reacted as completely as possible.

[0016] In fact, the applicant has found that due to the high activity of PPDI, when PPDI is used to react with polyols to prepare component B, there must be a phenomenon of PPDI self-polymerization. In addition, in order to completely react the polyols as much as possible, an excessive amount of PPDI needs to be added during the feeding (the reason for this feeding has been explained above). This results in the presence of residual free PPDI monomers in component B after the reaction is completed, and these free PPDI monomers will continue to self-polymerize in component B. This makes the degree of self-polymerization of free PPDI monomers in component B different with the storage time, resulting in unstable viscosity of component B, which will change with the storage time, and then the quality and performance of the sole products produced are unstable. Even for the same batch of sole stock solution, the quality and performance of the sole products produced are different due to different production times. This does not meet the company's requirements for stable production. In addition, if the storage time of component B is too long, the degree of self-polymerization of free PPDI monomers in component B is too high, and cross-linking is excessive, which will reduce the quality and performance of the final sole products. This is even more undesirable for the company.

[0017] To this end, the applicant proposed the PPDI-based sole stock solution of the present invention, strictly limited the preparation method of component B, required that PPDI can only be added in excess of 1%-10% when feeding, and cannot be more excessive, otherwise the excessive free PPDI monomer will be difficult to handle, and on this basis, the following technical route is specially proposed: after the oligomer diol 1 and PPDI are fully reacted, a trimerization catalyst is added to make the remaining free PPDI monomer quickly self-polymerize in a short time to a reasonable degree that is beneficial to the improvement of the quality and performance of the final sole product, that is, the self-polymerization is accelerated in advance, and then an inhibitor is added to deactivate the trimerization catalyst to inhibit the subsequent self-polymerization process. In this way, not only the production efficiency of component B can be improved, but also the viscosity of the obtained component B can be kept stable for a long time, and the shelf life of component B in actual production can be extended, so that the company can plan production tasks more flexibly, ensure the quality and performance stability of the sole products, and at the same time, the quality and performance of the sole products can be significantly improved.

[0018] In summary, the present invention limits the content of PPDI free monomers in the B component of the sole stock solution through a specific process, and quickly completes the self-polymerization reaction of the free PPDI in a short time, thereby improving the stability of the B component, further optimizing the formula composition of the sole stock solution, and preparing a PPDI-based sole stock solution with excellent rebound, compression deformation and tearing properties.

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

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

[0021] In the preparation method of the B component, the oligomer diol 1 can be reacted with PPDI at 50-70° C. under an inert atmosphere for 1-3 hours, such as 2 hours, after being dehydrated.

[0022] In the preparation method of the B component, the number average molecular weight of the oligomer 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 oligomer diol 1 may include at least one of polytetramethylene glycol, polypropylene glycol, and polyester diol. Further, the polyester diol may include at least one of the brands P1110, P1215, and P1309 of Meirui New Materials Co., Ltd.

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

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

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

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

[0028] In the preparation method of the B component, after adding the polymerization inhibitor, stirring is performed for 0.5-1 hour (eg, 0.7 hour, etc.) to obtain the B component.

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

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

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

[0032] In the raw material composition of the A component, 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 the A component, the amount of water can be 0.5%-2.5% of the mass of the oligomer diol 2, such as 1.5%, 1.8%, 2%, etc. In the PPDI-based sole stock solution system of the present invention, water can act as a foaming agent.

[0034] In the raw material composition of the A component, the foam leveling agent can be selected according to conventional methods in the art, for example, it can include a polysiloxane foam leveling agent.

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

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

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

[0038] In the raw material composition of the C component, 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] In the PPDI-based sole stock solution, the mass ratio of component A to component C can be 100:0.3-1, for example, 100:0.5, 100:0.8, etc.

[0040] In the PPDI-based sole stock solution, the mass ratio of component A to component B 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 method for preparing the PPDI-based shoe sole stock solution according to [1] comprises:

[0042] Mixing oligomer diol 2, a foam leveler, water and an optionally added chain extender at 50-70° C. to obtain component A;

[0043] The oligomer diol 1 is dehydrated and then fully reacted with PPDI under inert atmosphere at 50-70°C, wherein PPDI is added in excess of 1%-10% based on the theoretical complete reaction with the oligomer diol 1, and then the temperature is raised to 70-90°C, a trimerization catalyst is added, and the reaction is continued for 1-2 hours, and then an inhibitor is added to deactivate the trimerization catalyst to obtain component B;

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

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

[0046] [4] A polyurethane microporous elastomer obtained by foaming a material including the PPDI-based shoe sole stock solution described in [1].

[0047] [5] A method for preparing a polyurethane microporous elastomer, comprising: foaming the PPDI-based shoe sole stock solution described in [1] to obtain the polyurethane microporous elastomer.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] 1. Use PPDI to replace the traditional MDI to synthesize the sole stock solution. Due to the symmetrical and regular molecular structure of PPDI, it can form a denser hard segment micro-region in the product and produce a high degree of micro-phase separation, so that the shoe material prepared by the PPDI-based sole stock solution has better rebound and compression resistance.

[0050] 2. During the preparation of component B of the sole stock solution, a stable PPDI-based sole stock solution component B was prepared by limiting the free PPDI content and promoting the self-polymerization reaction of free PPDI. At the same time, the trimer produced by PPDI self-polymerization can provide a certain cross-linking structure in the shoe material production process, shorten the demolding time and improve the sole strength. DETAILED DESCRIPTION

[0051] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention. The operating methods in the following examples where no specific conditions are indicated are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0052] Unless otherwise specified, the molecular weight units in the following examples are all g / mol, the molecular weight of the polymers are all number-average molecular weights; the foam leveling agents are all commercially available polysiloxane foam leveling agents.

[0053] Embodiment 1:

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

[0055] (2) Preparation of component A: 100 g of polytetramethylene glycol with a molecular weight of 1800, 1 g of a foam leveler, and 1.5 g of water were mixed at 50-70° C. to obtain component A.

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

[0057] Component A and component C are mixed and stirred evenly in a mass ratio of 100:0.5, and then mixed and stirred with component B in a mass ratio of 100:140, injected into a mold, and foamed to obtain a polyurethane microcellular elastomer.

[0058] Embodiment 2:

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

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

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

[0062] Component A and component C are mixed and stirred evenly in a mass ratio of 100:0.8, and then mixed and stirred with component B in a mass ratio of 100:200, injected into a mold, and foamed to obtain a polyurethane microcellular elastomer.

[0063] Embodiment 3:

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

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

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

[0067] Component A and component C are mixed and stirred evenly in a mass ratio of 100:0.3, and then mixed and stirred with component B in a mass ratio of 100:170, injected into a mold, and foamed to obtain a polyurethane microcellular elastomer.

[0068] Embodiment 4:

[0069] (1) Preparation of component B: 500 g of P1215 with a molecular weight of 1500 was stirred for 1-2 h at a temperature of 100-120 ° C and a vacuum degree of 0.08-0.1 MPa to remove water, then cooled to 50 ° C and added with 115 g of PPDI. The mixture was stirred for reaction for 2 h under nitrogen protection, then heated to 70 ° C and added with 0.07 g of trimerization catalyst TMR-2. The reaction was continued for 2 h, and 0.08 g of inhibitor dibutyl phosphate was added and stirred for 1 h to obtain component B.

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

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

[0072] Component A and component C are mixed and stirred evenly in a mass ratio of 100:0.8, and then mixed and stirred with component B in a mass ratio of 100:210, injected into a mold, and foamed to obtain a polyurethane microcellular elastomer.

[0073] Embodiment 5:

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

[0075] (2) Preparation of component A: 100 g of P1220 with a molecular weight of 2000, 5 g of EG, 1 g of a foam leveler and 1 g of water were mixed at 50-70° C. to obtain component A.

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

[0077] Component A and component C are mixed and stirred evenly in a mass ratio of 100:1, and then mixed and stirred with component B in a mass ratio of 100:170, injected into a mold, and foamed to obtain a polyurethane microcellular elastomer.

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

[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 160 g, and the theoretical free amount of PPDI is 0% at this time.

[0080] Comparative Example 3: The method of Comparative Example 3 is basically the same as that of Example 1, except that component B is prepared by stirring 500 g of polytetrahydrofuran ether glycol with a molecular weight of 1000 for 1-2 h to remove water at a temperature of 100-120 ° C and a vacuum degree of 0.08-0.1 MPa, then cooling to 50 ° C, adding 176 g of PPDI, stirring and reacting for 3 h under nitrogen protection to obtain component B, and component B is immediately used to prepare a polyurethane microporous elastomer. The experiment found that the viscosity of component B in Comparative Example 3 increased significantly after being left for a period of time, and the gel was solidified after 30 days.

[0081] Table 1 shows the performance test results of the microporous elastomers prepared in various embodiments and comparative examples.

[0082] Table 1

[0083]

[0084] Comparing Comparative Example 1 with Example 1, the tear strength and compression deformation performance of Comparative Example 1 are both deteriorated, indicating that too much PPDI (>10%) will have an adverse effect on the microporous elastomer.

[0085] Comparison of Comparative Example 2 with Example 1 shows that Example 1 has better tear strength, compression deformation performance and rebound performance, indicating that a proper excess of PPDI (1%-10%) is beneficial to improving the performance of microporous elastomers.

[0086] Comparison of Comparative Example 3 with Example 1 shows that component B of Comparative Example 3 shows increased viscosity and even gelation after long-term storage, indicating that the addition of the trimerization catalyst and the inhibitor of the present invention can greatly improve the stability of the sole stock solution.

[0087] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. A PPDI-based sole stock solution, characterized in that: It includes component A, component B and component C; The preparation method of component B comprises: dehydrating oligomer diol 1 and reacting it with PPDI under inert atmosphere at 50-70° C., wherein PPDI is added in excess of 1%-10% according to the theoretical complete reaction with oligomer diol 1, then heating to 70-90° C., adding trimerization catalyst and continuing reaction for 1-2 hours, then adding inhibitor to deactivate the trimerization catalyst, and obtaining component B; The raw material composition of component A includes oligomer diol 2, a foam leveler and water, and a chain extender which may be optionally added; The raw material composition of the C component includes a catalyst.

2. The PPDI-based sole stock solution according to claim 1, characterized in that In the preparation method of the B component: The dehydration process of the oligomer diol 1 comprises: removing water from the oligomer diol 1 at a temperature of 100-120° C. and a vacuum degree of 0.08-0.1 MPa; the dehydration time is 1-2 hours; The oligomer diol 1 is dehydrated and reacted with PPDI under an inert atmosphere at 50-70° C. for 1-3 hours; The number average molecular weight of the oligomer diol 1 is 800-1500 g / mol; The oligomer diol 1 includes at least one of polytetramethylene glycol, polypropylene glycol, and polyester diol, wherein the polyester diol includes at least one of the brands P1110, P1215, and P1309 of Meirui New Materials Co., Ltd.; The trimerization catalyst includes one or more of 2-hydroxy-N,N,N-trimethyl-1-propylamine formate, potassium 2-ethylhexanoate, 2-hydroxypropyltrimethylisooctanoate ammonium salt, and tributylphosphine; The trimerization catalyst is used in an amount of 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 trimerization catalyst added; After adding the polymerization inhibitor, stirring is carried out for 0.5-1 hour to obtain component B.

3. The PPDI-based sole stock solution according to claim 1, characterized in that: The raw material composition of the A component: The mass ratio of oligomer polyol 2, chain extender, water and foam leveling agent is 100: 0-10: 0.5-2.5: 0.5-2; The number average molecular weight of the oligomer diol 2 is 1500-4000 g / mol; The oligomer diol 2 includes at least one of polytetramethylene glycol and polyester diol, wherein the polyester diol includes at least one of 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 a polysiloxane foam leveling agent.

4. The PPDI-based sole stock solution according to claim 1 or 3, characterized in that: The preparation method of component A comprises: mixing the oligomer diol 2, a foam leveler, water and a chain extender which may be added selectively at 50-70° C. to obtain component A.

5. The PPDI-based sole stock solution according to claim 1, characterized in that: The raw material composition of the C component: The catalyst includes an organic metal catalyst and an amine catalyst; The mass ratio of the organic metal catalyst to the amine catalyst is 100:20-100; The organic metal catalyst includes at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, zinc isooctanoate, and bismuth isooctanoate; The amine catalyst includes at least one of triethylenediamine, tetramethyldiethylenetriamine, N,N-dimethyldiethanolamine, bismorpholinyldiethyl ether, and bis(dimethylaminoethyl) ether.

6. The PPDI-based sole stock solution 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 the PPDI-based shoe sole stock solution according to any one of claims 1 to 6, characterized in that: include: Mixing oligomer diol 2, a foam leveler, water and an optionally added chain extender at 50-70° C. to obtain component A; The oligomer diol 1 is dehydrated and then fully reacted with PPDI under inert atmosphere at 50-70°C, wherein PPDI is added in excess of 1%-10% based on the theoretical complete reaction with the oligomer diol 1, and then the temperature is raised to 70-90°C, a trimerization catalyst is added, and the reaction is continued for 1-2 hours, and then an inhibitor is added to deactivate the trimerization catalyst to obtain component B; Component A and component C are mixed evenly and then mixed with component B to obtain the PPDI-based sole stock solution.

8. Use of the PPDI-based sole stock solution according to any one of claims 1 to 6 in preparing soles.

9. A polyurethane microcellular elastomer, characterized in that: The shoe sole product is prepared by foaming a material including the PPDI-based shoe sole stock solution described in any one of claims 1 to 6.

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

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