CN113583286A - PU (polyurethane) material sole for women's shoes and preparation method thereof - Google Patents

Abstract

The application discloses the technical field of sole materials, and particularly discloses a PU material sole for ladies and a preparation method thereof. The PU material sole for the ladies consists of the following raw materials in parts by weight: 30-50 parts of polyol, 0.5-1.5 parts of antioxidant, 0.2-0.6 part of foaming agent, 40-50 parts of isocyanate, 2-6 parts of cross-linked body, 3-9 parts of hardener and 8-16 parts of elastomer; the elastomer comprises a styrene-isoprene block copolymer; the preparation method comprises the following steps: s1, primary mixing; s2, secondary mixing; s3, blending. The PU material sole for the ladies shoes can be used for improving the resilience of the polyurethane sole, so that the sole is not easy to shrink after long-term use by people, and the wearing comfort and the shoe attractiveness are improved; in addition, the preparation method has the advantages of simple operation and wide application.

Description

PU (polyurethane) material sole for women's shoes and preparation method thereof

Technical Field

The application relates to the technical field of sole materials, in particular to a PU material sole for women's shoes and a preparation method thereof.

Background

PU, polyurethane, is a high molecular compound, and is known as polyurethane. Polyurethanes fall into the two main categories of polyester and polyether. Polyurethane has the characteristics of wear resistance, folding resistance, oil resistance, chemical resistance and the like, and is often used for manufacturing soles. Polyurethane shoe materials are synthetic resins for shoes which are developed rapidly, and are widely used for producing casual shoes, sports shoes, working shoes, sandals and the like. Some of the unique properties of polyurethane footwear are missing from other footwear materials.

Women's shoes are an indispensable item in the daily dress collocation of women nowadays. Beauty and comfort are two important indicators of women's shoes, and the soles of a large number of women's shoes are also made of polyurethane. In order to reduce the cost of shoe material suppliers, the shoe material suppliers generally need to reduce the density of polyurethane when preparing soles, and the low-density polyurethane has the advantages of soft feel, comfort in wearing, warmth retention, skid resistance and simpler processing and forming. However, since the density of the low-density polyurethane is low, when a user wears a sole made of the low-density polyurethane, the sole deforms greatly, and if the rebound resilience of the polyurethane is poor, the sole is easily shrunken after the user wears the shoe for a long time, which leads to a reduction in the wearing comfort and the aesthetic property of the shoe.

Disclosure of Invention

In order to improve the resilience of the polyurethane sole, the sole is not easy to shrink after people use for a long time, and the wearing comfort and the attractiveness of the shoe are improved, the application provides the PU material sole for the ladies and the preparation method thereof.

The application provides a PU material sole for woman's shoe and preparation method adopts following technical scheme:

the PU material sole for the women's shoes and the preparation method thereof are characterized by comprising the following raw materials in parts by weight: 30-50 parts of polyol, 0.5-1.5 parts of antioxidant, 0.2-0.6 part of foaming agent, 40-50 parts of isocyanate, 2-6 parts of cross-linked body, 3-9 parts of hardener and 8-16 parts of elastomer; the elastomer comprises a styrene-isoprene block copolymer.

By adopting the technical scheme, the sole with excellent performance can be prepared by adding the polyalcohol, the isocyanate and other auxiliary agents. The elastomer is added into the raw material of the sole, and the elastomer comprises the styrene-isoprene block copolymer which has good fluidity and rebound resilience, and the styrene-isoprene block copolymer is added into the raw material of the sole, so that the rebound resilience of the sole can be effectively improved, and the comfort degree of a wearer is improved.

Preferably, the styrene-isoprene block copolymer has a star-shaped structure, and the preparation method of the star-shaped styrene-isoprene block copolymer comprises the following steps:

(1) taking 10-16 parts by weight of cyclohexane solution with the mass fraction of 5-15%, 4-8 parts by weight of n-butyl lithium, 8-12 parts by weight of styrene, 3-7 parts by weight of leacheate, 8-16 parts by weight of coupling agent, 2-6 parts by weight of terminating agent and 50-90 parts by weight of absolute ethyl alcohol; under an oxygen-free environment, mixing and stirring a cyclohexane solution with the mass fraction of 5-15% and n-butyllithium, adding styrene, and continuously mixing and stirring to obtain a reaction solution;

(2) adding the leacheate and half of the coupling agent by weight into the reaction solution obtained in the step (1) to obtain intermediate solution, and adding the remaining half of the coupling agent by weight and all the terminating agents into the intermediate solution to obtain glue solution;

(3) mixing the glue solution obtained in the step (2) with absolute ethyl alcohol, and standing for 4-8h to obtain standing liquid;

(4) and filtering the standing liquid, taking filter residues, drying the filter residues, and grinding to obtain the star-shaped styrene-isoprene block copolymer.

By adopting the technical scheme, the isoprene-styrene monomer is generated in the step (1); adding a terminating agent in the step (2) to obtain a glue solution containing the star-shaped styrene-isoprene block copolymer, and adding the coupling agent twice to improve the coupling efficiency; separating out the star styrene-isoprene block copolymer in absolute ethyl alcohol through the step (3); and (4) preparing the star-shaped styrene-isoprene block copolymer. Because the molecular chain of the star polymer is not easy to break, the molecular weight is not easy to reduce so as to keep the good shear stability and the fluidity of the styrene-isoprene block copolymer, and the good fluidity enables the styrene-isoprene block copolymer to be more uniformly dispersed in the sole raw material, thereby improving the resilience of the sole.

Preferably, the coupling agent comprises divinylbenzene.

By adopting the technical scheme, compared with other coupling agents, the divinylbenzene can generate an infusible polymer with a three-dimensional structure during copolymerization, so that the stability of the divinylbenzene can be effectively maintained, and the coupling efficiency is improved.

Preferably, the elastomer also comprises nano calcium carbonate, and the elastomer is compounded by styrene-isoprene block copolymer and nano calcium carbonate according to the mass ratio of (90-200): 1.

By adopting the technical scheme, the elastic shoe sole has the advantages that the trace nano calcium carbonate is added into the elastic body, and the added amount of the nano calcium carbonate is trace, so that the rebound resilience of the shoe sole is not easily influenced greatly. In addition, the nano calcium carbonate can play a role in toughening and reinforcing the sole, and the tear strength of the sole is improved, so that the toughness of the sole is improved, cracks are not easy to generate on the sole, and the durability of the sole is further improved.

Preferably, the styrene-isoprene block copolymer and the nano calcium carbonate are compounded to form the elastomer with the core-shell structure, the core structure of the core-shell structure is the nano calcium carbonate, and the shell structure of the core-shell structure is the styrene-isoprene block copolymer.

By adopting the technical scheme, the nano calcium carbonate is coated by the styrene-isoprene segmented copolymer to form a structure similar to a hard core and a soft shell, and the styrene-isoprene segmented copolymer has good fluidity, so that the styrene-isoprene segmented copolymer is used as the shell structure to keep the fluidity of the elastomer, the elastomer has good compatibility with other materials of the sole, and the resilience and the toughness of the sole are further improved.

Preferably, the styrene-isoprene block copolymer is a modified styrene-isoprene block copolymer modified by maleic anhydride grafting.

By adopting the technical scheme, after the styrene-isoprene block copolymer is grafted with the maleic anhydride, the maleic anhydride with larger polarity is easy to react with CO on the surface of the polar nano calcium carbonate₃ ^2-Generates stable chemical bond with OH < - > and forms ion-dipole effect with calcium ions at the same time, further improves the toughness between the styrene-isoprene block copolymer and the nano calcium carbonateThe stability of the interface layer further improves the toughness of the sole.

Preferably, the crosslinking body comprises dicumyl peroxide and triallyl isocyanurate, and the mass ratio of the dicumyl peroxide to the triallyl isocyanurate is (6-10) to (1-3).

By adopting the technical scheme, the dicumyl peroxide can enable linear molecules of the sole raw material to generate chemical bonds, so that the linear molecules are mutually connected to form a net structure, and the toughness and resilience of the sole are improved. The triallyl isocyanurate has the promoting effect, promotes the linear molecules of the sole raw material to form a net structure, and accelerates the reaction speed.

The second aspect, the application provides a preparation method of PU material sole for woman's shoes, adopts following technical scheme:

a preparation method of PU material soles for women's shoes comprises the following preparation steps:

s1, primary mixing: according to the formula, mixing and stirring the polyol and the isocyanate at the rotating speed of 400-600r/min for 30-40min to obtain a first mixture;

s2, secondary mixing: mixing and stirring the antioxidant, the hardening agent and the elastomer at the rotating speed of 200-300r/min for 6-10min to obtain a second mixture;

s3, blending: and melting and mixing the first mixture, the second mixture, the cross-linking body and the foaming agent in a double-screw extruder, extruding the mixture in a mould, pressing and molding the mixture, and drying the mixture to obtain the PU material sole for the ladies shoes.

By adopting the technical scheme, the polyol and the isocyanate which are more in parts by weight are uniformly mixed by primary mixing and stirring at medium speed; the secondary mixing is carried out at a low speed to ensure that the antioxidant, the hardening agent and the elastomer in a small amount by weight are uniformly mixed; in the blending step, under the action of a cross-linking agent, a stable network structure is formed between the elastomer and the first mixture, so that the rebound resilience and the rest performance of the sole are improved, and finally, under the action of a foaming agent, the PU material sole for the ladies shoes with low density and high rebound resilience is prepared.

In summary, the present application has the following beneficial effects:

1. the sole with excellent performance can be prepared by adding the polyalcohol, the isocyanate and other auxiliary agents. The elastomer is added into the raw material of the sole, and the elastomer comprises the styrene-isoprene block copolymer which has good fluidity and rebound resilience, so that the rebound resilience of the sole can be effectively improved by adding the styrene-isoprene block copolymer into the raw material of the sole, and the comfort degree of a wearer is improved;

2. the ethylene-isoprene segmented copolymer is of a star-shaped structure, and the molecular chain of the star-shaped polymer is not easy to break, so that the molecular weight is not easy to reduce, the good shear stability and the good fluidity of the styrene-isoprene segmented copolymer are maintained, and the styrene-isoprene segmented copolymer is uniformly dispersed in the sole raw material due to the good fluidity, so that the resilience of the sole is improved;

3. according to the method, a large amount of polyol and isocyanate are uniformly mixed by primary mixing and stirring at a medium speed; the secondary mixing is carried out at a low speed to ensure that the antioxidant, the hardening agent and the elastomer in a small amount by weight are uniformly mixed; in the blending step, under the action of a cross-linking agent, a stable network structure is formed between the elastomer and the first mixture, so that the rebound resilience and the rest performance of the sole are improved, and finally, under the action of a foaming agent, the PU material sole for the ladies shoes with low density and high rebound resilience is prepared.

Detailed Description

The present application will be described in further detail with reference to examples.

Table 1 apparatus according to embodiments of the present application

In the examples of the present application, the drugs used are shown in Table 2:

table 2 pharmaceutical products according to embodiments of the present application

Preparation of elastomer

Preparation example 1:

the present preparation example used a commercially available styrene-isoprene block copolymer as the elastomer.

Preparation example 2: the preparation example is prepared by the following method:

(1) mixing 10kg of cyclohexane solution with the mass fraction of 10% and 4kg of n-butyl lithium at the temperature of 60 ℃ and the rotating speed of 200r/min for 6min under an oxygen-free environment, adding 8kg of styrene, and continuously mixing and stirring for 4min to obtain a reaction solution;

(2) adding 3kg of tetrahydrofuran as an eluent and 4kg of divinylbenzene as a coupling agent into the reaction solution obtained in the step (1), continuously mixing and stirring for 15min at the rotating speed of 200r/min to obtain an intermediate solution, adding 4kg of the coupling agent and 2kg of a terminating agent into the intermediate solution, and continuously stirring for 10min at the rotating speed of 200r/min to obtain a glue solution;

(3) mixing the glue solution obtained in the step (2) with 50kg of absolute ethyl alcohol, and standing for 6 hours to obtain standing liquid;

(4) filtering the standing solution, taking filter residue, drying the filter residue at 80 ℃ for 10h, grinding and sieving with a 400-mesh sieve to obtain the star-shaped styrene-isoprene segmented copolymer, namely the elastomer.

Preparation example 3: the preparation example is prepared by the following method:

(1) mixing 13kg of cyclohexane solution with the mass fraction of 10% with 6kg of n-butyl lithium at the temperature of 60 ℃ and the rotating speed of 200r/min for 6min under an oxygen-free environment, adding 10kg of styrene, and continuously mixing and stirring for 4min to obtain a reaction solution;

(2) adding 5kg of tetrahydrofuran as an eluent and 6kg of divinylbenzene as a coupling agent into the reaction solution obtained in the step (1), continuously mixing and stirring for 15min at the rotating speed of 200r/min to obtain an intermediate solution, adding 6kg of the coupling agent and 4kg of a terminating agent into the intermediate solution, and continuously stirring for 10min at the rotating speed of 200r/min to obtain a glue solution;

(3) mixing the glue solution obtained in the step (2) with 70kg of absolute ethyl alcohol, and standing for 6 hours to obtain standing liquid;

(4) filtering the standing solution, taking filter residue, drying the filter residue at 80 ℃ for 10h, grinding and sieving with a 400-mesh sieve to obtain the star-shaped styrene-isoprene segmented copolymer, namely the elastomer.

Preparation example 4: the preparation example is prepared by the following method:

(1) under an oxygen-free environment, 16kg of cyclohexane solution with the mass fraction of 10 percent is taken to be mixed and stirred with 8kg of n-butyl lithium at the temperature of 60 ℃ and the rotating speed of 200r/min for 6min, and then 12kg of styrene is added to be continuously mixed and stirred for 4min to obtain reaction liquid;

(2) adding 7kg of tetrahydrofuran as an eluent and 8kg of divinylbenzene as a coupling agent into the reaction solution obtained in the step (1), continuously mixing and stirring for 15min at the rotating speed of 200r/min to obtain an intermediate solution, adding 8kg of the coupling agent and 6kg of a terminating agent into the intermediate solution, and continuously stirring for 10min at the rotating speed of 200r/min to obtain a glue solution;

(3) mixing the glue solution obtained in the step (2) with 90kg of absolute ethyl alcohol, and standing for 6 hours to obtain standing liquid;

(4) filtering the standing solution, taking filter residue, drying the filter residue at 80 ℃ for 10h, grinding and sieving with a 400-mesh sieve to obtain the star-shaped styrene-isoprene segmented copolymer, namely the elastomer.

Preparation example 5:

this production example differs from production example 3 in that this production example employs a commercially available coupling agent kh560 as a coupling agent instead of the coupling agent in production example 3.

Preparation example 6: the preparation example is prepared by the following method:

(1) mixing 13kg of cyclohexane solution with the mass fraction of 10% with 6kg of n-butyl lithium at the temperature of 60 ℃ and the rotating speed of 200r/min for 6min under an oxygen-free environment, adding 10kg of styrene, and continuously mixing and stirring for 4min to obtain a reaction solution;

(2) adding 5kg of tetrahydrofuran as an eluent and 6kg of divinylbenzene as a coupling agent into the reaction solution obtained in the step (1), continuously mixing and stirring for 15min at the rotating speed of 200r/min to obtain an intermediate solution, adding 6kg of the coupling agent and 4kg of a terminating agent into the intermediate solution, and continuously stirring for 10min at the rotating speed of 200r/min to obtain a glue solution;

(3) mixing the glue solution obtained in the step (2) with 70kg of absolute ethyl alcohol, and standing for 6 hours to obtain standing liquid;

(4) and filtering the standing liquid, taking filter residue, drying the filter residue at 80 ℃ for 10 hours, grinding and sieving with a 400-mesh sieve to obtain the star-shaped styrene-isoprene segmented copolymer.

(5) 2kg of star styrene-isoprene block copolymer and 0.02kg of nano calcium carbonate are mixed and stirred for 5min at the rotating speed of 200r/min to obtain a styrene-isoprene block copolymer/nano calcium carbonate complex, namely the elastomer.

Preparation example 7: the preparation example is prepared by the following method:

(1) mixing 13kg of cyclohexane solution with the mass fraction of 10% with 6kg of n-butyl lithium at the temperature of 60 ℃ and the rotating speed of 200r/min for 6min under an oxygen-free environment, adding 10kg of styrene, and continuously mixing and stirring for 4min to obtain a reaction solution;

(2) adding 5kg of tetrahydrofuran as an eluent and 6kg of divinylbenzene as a coupling agent into the reaction solution obtained in the step (1), continuously mixing and stirring for 15min at the rotating speed of 200r/min to obtain an intermediate solution, adding 6kg of the coupling agent and 4kg of a terminating agent into the intermediate solution, and continuously stirring for 10min at the rotating speed of 200r/min to obtain a glue solution;

(3) mixing and stirring the glue solution obtained in the step (2) and 0.02kg of nano calcium carbonate at the rotating speed of 200r/min for 5min to obtain an intermediate;

(4) mixing the intermediate in the step (3) with 70kg of absolute ethyl alcohol, and standing for 6 hours to obtain standing liquid;

(5) and filtering the standing liquid, taking filter residue, drying the filter residue at 80 ℃ for 10h, grinding and sieving with a 400-mesh sieve to obtain the styrene-isoprene segmented copolymer/nano calcium carbonate complex with the core-shell structure, namely the elastomer.

Preparation example 8: the preparation example is prepared by the following method:

(1) mixing 13kg of cyclohexane solution with the mass fraction of 10% with 6kg of n-butyl lithium at the temperature of 60 ℃ and the rotating speed of 200r/min for 6min under an oxygen-free environment, adding 10kg of styrene, and continuously mixing and stirring for 4min to obtain a reaction solution;

(2) adding 5kg of tetrahydrofuran as an eluent and 6kg of divinylbenzene as a coupling agent into the reaction solution obtained in the step (1), continuously mixing and stirring for 15min at the rotating speed of 200r/min to obtain an intermediate solution, adding 6kg of the coupling agent and 4kg of a terminating agent into the intermediate solution, and continuously stirring for 10min at the rotating speed of 200r/min to obtain a glue solution;

(3) mixing the glue solution obtained in the step (2) with 13kg of absolute ethyl alcohol, and standing for 6 hours to obtain standing liquid;

(4) filtering the standing liquid, taking filter residue, drying the filter residue at 80 ℃ for 10h, grinding and sieving with a 400-mesh sieve to obtain a star-shaped styrene-isoprene segmented copolymer;

(5) mixing and stirring 2kg of star-shaped styrene-isoprene block copolymer and 0.5kg of maleic anhydride at the rotating speed of 150r/min for 10min to obtain modified styrene-isoprene block copolymer;

(6) 2kg of modified styrene-isoprene block copolymer and 0.02kg of nano calcium carbonate are mixed and stirred for 5min at the rotating speed of 200r/min to obtain a modified styrene-isoprene block copolymer/nano calcium carbonate complex, namely the elastomer.

Preparation example of crosslinked Material

Preparation example 9: the preparation example is prepared by the following method:

6kg of dicumyl peroxide and 1kg of triallyl isocyanurate are mixed and stirred for 5min at the rotating speed of 120r/min to obtain the cross-linked body.

Preparation example 10: the preparation example is prepared by the following method:

8kg of dicumyl peroxide and 2kg of triallyl isocyanurate are mixed and stirred for 5min at the rotating speed of 120r/min to obtain the cross-linked body.

Preparation example 11: the preparation example is prepared by the following method:

10kg of dicumyl peroxide and 3kg of triallyl isocyanurate are mixed and stirred for 5min at the rotating speed of 120r/min to obtain the cross-linked body.

Preparation example 12: the difference between the present preparation example and preparation example 10 is that:

the crosslinked material of this preparation example contained only 8kg of dicumyl peroxide.

Examples

Example 1: preparation method of PU material sole for women's shoes

S1, primary mixing: 30kg of polyol, 0.5kg of antioxidant, 0.2kg of foaming agent, 40kg of isocyanate, 2kg of cross-linked body of preparation example 10, 3kg of hardener and 8kg of elastomer of preparation example 1 are taken; according to the formula, polyol and isocyanate are mixed and stirred for 30min at a medium speed of 400r/min to obtain a first mixture;

s2, secondary mixing: mixing and stirring the antioxidant, the hardening agent and the elastomer at a low speed of 200r/min for 6min to obtain a second mixture;

s3, blending: and melting and mixing the first mixture, the second mixture, the cross-linking body and the foaming agent in a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 300 ℃, the rotation speed of the double-screw extruder is 600r/min, extruding the mixture in a mould, and performing compression molding and drying to obtain the PU material sole for the ladies.

Example 2: preparation method of PU material sole for women's shoes

S1, primary mixing: taking 40kg of polyol, 1kg of antioxidant, 0.4kg of foaming agent, 45kg of isocyanate, 4kg of cross-linked body of preparation example 10, 6kg of hardener and 12kg of elastomer of preparation example 1; according to the formula, polyol and isocyanate are mixed and stirred for 30min at a medium speed of 400r/min to obtain a first mixture;

s2, secondary mixing: mixing and stirring the antioxidant, the hardening agent and the elastomer at a low speed of 200r/min for 6min to obtain a second mixture;

s3, blending: and melting and mixing the first mixture, the second mixture, the cross-linking body and the foaming agent in a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 300 ℃, the rotation speed of the double-screw extruder is 600r/min, extruding the mixture in a mould, and performing compression molding and drying to obtain the PU material sole for the ladies.

Example 3: preparation method of PU material sole for women's shoes

S1, primary mixing: taking 50kg of polyol, 1.5kg of antioxidant, 0.6kg of foaming agent, 50kg of isocyanate, 6kg of cross-linked body of preparation example 10, 9kg of hardening agent and 16kg of elastomer of preparation example 1; according to the formula, polyol and isocyanate are mixed and stirred for 30min at a medium speed of 400r/min to obtain a first mixture;

s2, secondary mixing: mixing and stirring the antioxidant, the hardening agent and the elastomer at a low speed of 200r/min for 6min to obtain a second mixture;

s3, blending: and melting and mixing the first mixture, the second mixture, the cross-linking body and the foaming agent in a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 300 ℃, the rotation speed of the double-screw extruder is 600r/min, extruding the mixture in a mould, and performing compression molding and drying to obtain the PU material sole for the ladies.

Examples 4 to 10: preparation method of PU material sole for women's shoes

Examples 4-10 differ from example 2 in the elastomers selected, as shown in table 3:

TABLE 3 Elastomers selected for use in examples 4-10

Examples 11 to 13: preparation method of PU material sole for women's shoes

Examples 11 to 13 differ from example 2 in the crosslinking species selected, the crosslinking species of preparation example 9 was selected for example 11, the crosslinking species of preparation example 11 was selected for example 12, and the crosslinking species of preparation example 12 was selected for example 13.

Comparative example

Comparative example 1: this comparative example differs from example 2 in that:

no elastomer was added to this comparative example.

Comparative example 2

The comparative example adopts a sole of 6502 model of Fushan Sanmei plastics Limited.

Performance test

1. Tear strength: the test was carried out in accordance with GB/T529-2008 "determination of tear Strength of vulcanized rubber or thermoplastic rubber (trouser, Right-Angle and crescent specimens").

2. The rebound resilience: the method is carried out according to the regulation of GB/T1681-1991 'determination of resilience of vulcanized rubber'.

TABLE 4 Performance test Table

The examples 1 to 3 are compared, and the differences of the examples 1 to 3 lie in the different proportions of the raw materials of the shoe PU material sole, the maximum tear strength and the highest rebound resilience of the example 2, and the best toughness and rebound resilience of the example 2, so the proportion of the raw materials in the example 2 is the best.

Example 4 was compared with example 1, and example 4 was different from example 1 in that the elastomer of preparation example 2 was used in example 4 to add to the raw material of shoe soles, while example 1 used the elastomer of preparation example 1. Preparation example 2 differs from preparation example 1 in that the elastomer of preparation example 2 is a styrene-isoprene block copolymer of a star-shaped structure, while the elastomer of preparation example 1 is a commercially available styrene-isoprene block copolymer. As the tear strength and the rebound resilience of the material are higher in example 4, the toughness and the rebound resilience of the material are better in example 4, and the star-structured styrene-isoprene block copolymer is better.

Examples 4-6 were compared, except that examples 4-6 were prepared in the order of examples 4-6 to prepare wear resistant bodies according to examples 5-7, except that examples 5-7 were prepared in different proportions of the raw materials for preparing the radial styrene-isoprene block copolymer, whereas example 5 was the most tear resistant and resilient, indicating that example 5 has the best toughness and resilience, and therefore example 5 has the best proportions of the raw materials for preparing the radial styrene-isoprene block copolymer.

Example 7 was compared with example 5, with example 7 differing from example 5 in that example 7 used the elastomer of preparation 5, whereas example 5 used the elastomer of preparation 3, with preparation 5 differing from preparation 3 in that preparation 5 used a commercially available coupling agent kh560 as the coupling agent instead of preparation 3. Example 5 is shown to have better toughness and resiliency due to its greater tear strength and higher rebound resilience, indicating that the coupling agent of the present application is better.

Example 8 was compared with example 5, and example 8 was different from example 4 in that the elastomer of example 8 was a styrene-isoprene block copolymer/nano calcium carbonate composite, and the elastomer of example 5 was a styrene-isoprene block copolymer. The resilience is similar to that of example 8 and example 5, while the tear strength of example 8 is higher, which indicates that the styrene-isoprene block copolymer/nano calcium carbonate composite is better used as an elastomer in the application.

Example 9 was compared with example 8, and example 9 and example 8 were different in that the elastomer of example 9 was a styrene-isoprene block copolymer/nano calcium carbonate composite having a core-shell structure, and the elastomer of example 8 was a styrene-isoprene block copolymer/nano calcium carbonate composite. The rebound rate of the example 9 is the same as that of the example 8, while the tear strength of the example 9 is higher, which shows that the styrene-isoprene block copolymer/nano calcium carbonate composite with the core-shell structure is better used as an elastomer in the application.

Example 10 was compared with example 8, and example 10 and example 8 were different in that the elastomer of example 10 was a modified styrene-isoprene block copolymer/nano calcium carbonate composite, and the elastomer of example 8 was a styrene-isoprene block copolymer/nano calcium carbonate composite. While the rebound rate of the example 10 is similar to that of the example 8, the tear strength of the example 10 is higher, which shows that the styrene-isoprene block copolymer/nano calcium carbonate composite with the core-shell structure is better used as an elastomer in the application.

Examples 2 and 11 to 12 were compared, examples 2 and 11 to 12 were different in the crosslinking agents used, and examples 11, 2 and 12 were prepared in the order of preparation examples 9 to 11. The cross-linked products of examples 9 to 11 were different in the ratio of dicumyl peroxide to triallyl isocyanurate, and the highest tear strength and the highest rebound resilience of example 2 indicated that the ratio of dicumyl peroxide to triallyl isocyanurate in the cross-linked product of example 2 was the best.

Example 13 was compared to example 2, with example 13, example 2 differing in that only dicumyl peroxide, and no triallyl isocyanurate, was present in the crosslinked body of example 13. The greater tear strength and higher resilience of example 2 indicates that the crosslinks are better in this application.

Finally, example 2 and comparative examples 1 to 2 were compared, and comparative example 1 was different from example 2 in that no elastomer was added in comparative example 1 and 6502 model number shoe sole of Foshan Sanmei plastics Co. The shoe soles of the present application are better because of the maximum tear strength and the highest rebound rate of example 2.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (8)

1. The utility model provides a PU material sole for woman's shoe, its characterized in that comprises the raw materials that contain following parts by weight:

30-50 parts of polyol;

0.5-1.5 parts of antioxidant;

0.2-0.6 part of foaming agent;

40-50 parts of isocyanate;

2-6 parts of a cross-linked body;

3-9 parts of a hardening agent;

8-16 parts of an elastomer; the elastomer comprises a styrene-isoprene block copolymer.

2. The PU material sole for women's shoes according to claim 1, wherein: the styrene-isoprene segmented copolymer is of a star-shaped structure, and the preparation method of the star-shaped styrene-isoprene segmented copolymer comprises the following steps:

(1) taking 10-16 parts by weight of cyclohexane solution with the mass fraction of 5-15%, 4-8 parts by weight of n-butyl lithium, 8-12 parts by weight of styrene, 3-7 parts by weight of leacheate, 8-16 parts by weight of coupling agent, 2-6 parts by weight of terminating agent and 50-90 parts by weight of absolute ethyl alcohol; under an oxygen-free environment, mixing and stirring a cyclohexane solution with the mass fraction of 5-15% and n-butyllithium, adding styrene, and continuously mixing and stirring to obtain a reaction solution;

(2) adding the leacheate and half of the coupling agent by weight into the reaction solution obtained in the step (1) to obtain intermediate solution, and adding the remaining half of the coupling agent by weight and all the terminating agents into the intermediate solution to obtain glue solution;

(3) mixing the glue solution obtained in the step (2) with absolute ethyl alcohol, and standing for 4-8h to obtain standing liquid;

(4) and filtering the standing liquid, taking filter residues, drying the filter residues, and grinding to obtain the star-shaped styrene-isoprene block copolymer.

3. The PU material sole for women's shoes according to claim 2, wherein: the coupling agent includes divinylbenzene.

4. The PU material sole for women's shoes according to claim 1, wherein: the elastomer also comprises nano calcium carbonate, and the elastomer is compounded by styrene-isoprene segmented copolymer and nano calcium carbonate according to the mass ratio of (90-200) to 1.

5. The PU material sole for women's shoes according to claim 4, wherein: the styrene-isoprene block copolymer and the nano calcium carbonate are compounded to form the elastomer with the core-shell structure, the core structure of the core-shell structure is the nano calcium carbonate, and the shell structure of the core-shell structure is the styrene-isoprene block copolymer.

6. The PU material sole for women's shoes according to claim 4, wherein: the styrene-isoprene block copolymer is a modified styrene-isoprene block copolymer obtained by grafting and modifying maleic anhydride.

7. The PU material sole for women's shoes according to claim 1, wherein: the crosslinking agent comprises dicumyl peroxide and triallyl isocyanurate, and the mass ratio of the dicumyl peroxide to the triallyl isocyanurate is (6-10) to (1-3).

8. The method for preparing PU material sole for women's shoes according to any one of claims 1-7, wherein: the preparation method comprises the following preparation steps:

s1, primary mixing: according to the formula, polyol and isocyanate are mixed and stirred at the medium speed of 400-600r/min for 30-40min to obtain a first mixture;

s2, secondary mixing: mixing and stirring the antioxidant, the hardening agent and the elastomer at a low speed of 200-300r/min for 6-10min to obtain a second mixture;

s3, blending: and melting and mixing the first mixture, the second mixture, the cross-linking body and the foaming agent in a double-screw extruder, extruding the mixture in a mould, pressing and molding the mixture, and drying the mixture to obtain the PU material sole for the ladies shoes.