CN112457536B

CN112457536B - Preparation method of anti-skid wear-resistant boots

Info

Publication number: CN112457536B
Application number: CN202011347136.1A
Authority: CN
Inventors: 姚金海; 林清香; 方常毅
Original assignee: Putian Hanjiang Yifeng Footwear Co ltd
Current assignee: Putian Hanjiang Yifeng Footwear Co ltd
Priority date: 2020-11-26
Filing date: 2020-11-26
Publication date: 2023-03-17
Anticipated expiration: 2040-11-26
Also published as: CN112457536A

Abstract

The application relates to the field of shoes, and particularly discloses a preparation method of an anti-skidding wear-resistant boot. A preparation method of the antiskid and wear-resistant boot comprises the following steps: s1, banburying natural rubber, TPEE, carbon fiber powder, nano clay and stearic acid for 10 to 15min, and then placing at room temperature for 18 to 24h to obtain master batch; s2, adding an anti-aging agent and an accelerator into the master batch for banburying, continuing banburying for 3 to 7min, then tabletting, and cooling for 18 to 24h to obtain a rubber sheet; s3, adding sulfur into the raw rubber sheet, and then vulcanizing and forming to obtain a boot sole; and S4, bonding the boot bottom and the boot upper to obtain the boot. The preparation method has the advantages that the boots have good anti-skid performance and wear resistance.

Description

Preparation method of anti-skid wear-resistant boots

Technical Field

The application relates to the field of shoes, in particular to a manufacturing method of an anti-skid and wear-resistant boot.

Background

Boots are cylindrical shoes with upper parts higher than ankle bones, and the heat of choosing boots is continuously increased along with the improvement of living standard and aesthetic standard of people, so manufacturers can put out boots with good quality and durability to attract customers, and the quality and durability of the boots are usually judged according to the anti-skid and wear-resisting performances of boot bottoms.

The anti-skid performance of the boot sole is embodied in the gripping force and the friction force between the boot sole and the ground, and the boot sole with good anti-skid performance can reduce the falling condition of a wearer due to wet and slippery ground and protect the body of the wearer; the wear resistance of the boot sole is embodied in the wear caused by the friction between the boot sole and the ground, and the boot sole with good wear resistance can prolong the service life of the boot sole.

The sole of the boot is generally made of natural rubber, and in order to improve the wear resistance of the sole, related technicians add fillers into the rubber to reinforce and increase the hardness of the sole to improve the wear resistance of the sole, however, the hardness is not an ideal reference value for influencing the friction force between the sole and the ground, and the increase of the hardness cannot well improve the anti-skid performance of the sole and needs to be improved.

Disclosure of Invention

In order to enable the boots to have good anti-skid performance and wear-resisting performance, the application provides a preparation method of the anti-skid wear-resisting boots.

The preparation method of the antiskid wear-resistant boot adopts the following technical scheme:

a preparation method of the antiskid wear-resistant boot comprises the following steps:

s1, banburying natural rubber, TPEE, carbon fiber powder, nano clay and stearic acid for 10 to 15min, and then standing at room temperature for 18 to 24h to obtain master batch;

s2, adding an anti-aging agent and a promoter into the master batch for banburying, continuing banburying for 3 to 7min, then tabletting, and cooling for 18 to 24h to obtain a rubber sheet;

s3, adding sulfur into the raw rubber sheet, and then vulcanizing and forming to obtain a boot sole;

and S4, bonding the boot bottom and the boot upper to obtain the boot.

By adopting the technical scheme, as the TPEE and the carbon fiber powder are adopted, and the TPEE is a thermoplastic polyester elastomer, the interaction force between the molecular chain segments in the boot sole is improved, the adhesive friction force between the boot sole and the contact surface is improved, and the anti-skid property of the boot is improved; the nano-clay reinforces the natural rubber, improves the wear resistance of the boot sole, and has better compatibility with TPEE, so that the structural stability of the boot sole is better, and the manufactured boot has good anti-skid performance and wear resistance.

Preferably, in the step S1, the banburying temperature is 100 to 110 ℃, and in the step S2, the banburying temperature is 115 to 125 ℃.

By adopting the technical scheme, the temperature range is favorable for fully mixing all the raw materials of the boot sole so as to achieve good anti-skid performance and wear resistance.

Preferably, in the step S3, the vulcanization temperature is 130 to 150 ℃, the vulcanization time is 8 to 12min, and the vulcanization pressure is 20 to 25Mpa.

By adopting the technical scheme, the vulcanization reaction parameters are more stable after the boot sole is molded, and the wear resistance is improved.

Preferably, the weight ratio of the natural rubber, the TPEE, the carbon fiber powder, the nano clay, the stearic acid, the anti-aging agent, the accelerator and the sulfur is 100 (40) - (60): 4) - (7): 11) - (18): 0.5) - (0.8): 0.6) - (0.8): 1) - (1.5): 1) - (2).

By adopting the technical scheme, the combination amount of the TPEE and the natural rubber is higher, and the anti-skid performance of the boot sole is improved.

Preferably, before the step S1, the method further comprises a step S1A: TPEE, toluene diisocyanate and acetone are stirred for 2 to 3 hours at the temperature of 60 to 70 ℃, the weight ratio of the TPEE to the toluene diisocyanate to the acetone is 10 (1.6 to 2) (20 to 30), after stirring, solid is obtained by filtration, and the pretreated TPEE is obtained by drying.

By adopting the technical scheme, the TPEE is pretreated by the toluene diisocyanate, and the toluene diisocyanate is combined with the active groups on the surface of the TPEE, so that the compatibility of the TPEE and the natural rubber is improved, and the anti-skid performance of the shoe sole is improved.

Preferably, before the step S1, the method further includes a step S1B: mixing and stirring the nano clay, the KH570 and the ethanol for 0.5 to 1h, wherein the weight ratio of the nano clay to the KH570 to the ethanol is 10 (0.5 to 0.8) to 25 to 35, filtering after stirring to obtain a solid, and drying to obtain the pretreated nano clay.

By adopting the technical scheme, the KH570 is used for pretreating the nano-clay, so that the dispersibility of the nano-clay in the natural rubber is improved, and the nano-clay has a reinforcing effect on the natural rubber.

Preferably, in the step S1, the banburying raw materials further comprise isopropyl palmitate, and the weight ratio of the natural rubber to the isopropyl palmitate is 100 (15 to 21).

By adopting the technical scheme, the isopropyl palmitate can improve the compatibility of the TPEE and the natural rubber, and further promote the improvement of the antiskid performance of the TPEE to the boot sole.

Preferably, in the S1 step, TPEE, carbon fiber powder, nanoclay and isopropyl palmitate are premixed into a premix, and then banburying together with natural rubber and stearic acid.

By adopting the technical scheme, the nanoclay is firstly dispersed in the isopropyl palmitate, so that the subsequent dispersion of the nanoclay is promoted, the wear resistance is improved, the combination of the isopropyl palmitate and the TPEE is promoted, the combination of the TPEE and the natural rubber is improved, and the anti-skid property is improved.

Preferably, the antioxidant is antioxidant DNP.

By adopting the technical scheme, the aging of the boot sole is delayed, and the service life of the boot sole is prolonged.

Preferably, the promoter CZ and the promoter DM are selected from the group consisting of promoters CZ and DM in a weight ratio of 1 (0.5 to 1).

By adopting the technical scheme, the crosslinking reaction of the sulfur and the natural rubber is accelerated, and the vulcanization is promoted.

The beneficial effect of this application:

1. TPEE and carbon fiber powder are added to improve the adhesive friction force between the boot bottom and the contact surface, so that the anti-skid performance of the boot is improved; the nano-clay reinforces the natural rubber, improves the wear resistance of the boot sole, and has better compatibility with TPEE, so that the boot sole has better structural stability, and the manufactured boot has better skid resistance and wear resistance.

2. Isopropyl palmitate is preferably adopted in the application, and the compatibility of TPEE and natural rubber is improved, so that the improvement of the antiskid performance of TPEE to the shoe sole is further promoted.

Detailed Description

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

The natural rubber is selected from standard rubber SCR5;

TPEE selects a medium petrochemical TX555 model;

the carbon fiber powder is purchased from Yaowang friction material factories in Changzhou, and the fineness is 900 to 950 meshes;

the nano-clay is selected from Orotai product processing factories in Lingshu county, and the fineness is 300 to 325 meshes.

Examples

Example 1

A preparation method of an antiskid wear-resistant boot comprises the following steps:

s1, putting 10kg of natural rubber, 4kg of TPEE, 0.6kg of carbon fiber powder, 1.1kg of nano clay and 0.05kg of stearic acid into an internal mixer, carrying out internal mixing at the temperature of 100 ℃ for 10min, and then standing at room temperature for 24h to obtain master batch;

s2, putting the master batch into an internal mixer again, adding 0.08kg of anti-aging agent DNP, 0.05kg of accelerator CZ and 0.05kg of accelerator DM, carrying out internal mixing at the temperature of 120 ℃ for 3min, then tabletting, and cooling for 24h to obtain a raw rubber sheet;

s3, adding 0.1kg of sulfur into the raw rubber sheet, and then putting the raw rubber sheet into a vulcanization forming machine for vulcanization forming, wherein the vulcanization temperature is 130 ℃, the vulcanization time is 8min, and the vulcanization pressure is 20Mpa, so that a boot sole is obtained;

and S4, bonding the boot bottom and the boot upper to obtain the boot.

Example 2

s1, putting 10kg of natural rubber, 6kg of TPEE, 0.4kg of carbon fiber powder, 1.8kg of nano clay and 0.08kg of stearic acid into an internal mixer, carrying out internal mixing at the temperature of 110 ℃ for 15min, and then standing at room temperature for 18h to obtain master batch;

s2, putting the master batch into an internal mixer again, adding 0.06kg of anti-aging agent DNP, 0.1kg of accelerator CZ and 0.05kg of accelerator DM, carrying out internal mixing at 115 ℃ for 5min, then tabletting, and cooling for 24h to obtain a rubber sheet;

s3, adding 0.1kg of sulfur into the raw rubber sheet, and then putting the raw rubber sheet into a vulcanization forming machine for vulcanization forming, wherein the vulcanization temperature is 150 ℃, the vulcanization time is 12min, and the vulcanization pressure is 20Mpa, so as to obtain a boot sole;

and S4, bonding the boot bottom and the boot upper to obtain the boot.

Example 3

A preparation method of an anti-skid wear-resistant boot comprises the following steps:

s1, putting 10kg of natural rubber, 5kg of TPEE, 0.7kg of carbon fiber powder, 1.4kg of nano clay and 0.07kg of stearic acid into an internal mixer, carrying out internal mixing at the temperature of 110 ℃ for 15min, and then standing at room temperature for 24h to obtain master batch;

s2, putting the master batch into an internal mixer again, adding 0.07kg of antioxidant DNP, 0.075kg of accelerator CZ and 0.075kg of accelerator DM, carrying out internal mixing at 125 ℃ for 7min, then tabletting, and cooling for 18h to obtain a rubber sheet;

s3, adding 0.2kg of sulfur into the raw rubber sheet, and then putting the raw rubber sheet into a vulcanization forming machine for vulcanization forming, wherein the vulcanization temperature is 140 ℃, the vulcanization time is 12min, and the vulcanization pressure is 25Mpa, so that a boot sole is obtained;

and S4, bonding the boot bottom and the boot upper to obtain the boot.

The raw materials and parameter differences for examples 1 to 3 are shown in table 1.

TABLE 1

	Example 1	Example 2	Example 3
				Natural rubber (kg)	10	10	10
TPEE(kg)	4	6	5
				Carbon fiber powder (kg)	0.6	0.4	0.7
Nanoclay (kg)	1.1	1.8	1.4
				Stearic acid (kg)	0.05	0.08	0.07
Antioxidant DNP (kg)	0.08	0.06	0.07
				Accelerator CZ (kg)	0.05	0.1	0.075
Accelerator DM (kg)	0.05	0.05	0.075
				Sulfur (kg)	0.1	0.1	0.2
S1 Banbury mixing temperature (DEG C)	100	110	110
				S1 Banbury mixing time (min)	10	15	15
S1 Cooling time (h)	24	18	24
				S2 internal mixing temperature (DEG C)	120	115	125
S2 mixing time (min)	3	5	7
				S2 Cooling time (h)	24	24	18
S3 vulcanization time (min)	8	12	12
				S3 vulcanization temperature (. Degree. C.)	130	150	140
S3 vulcanization pressure (MPa)	20	20	25

Example 4

The present embodiment is different from embodiment 3 only in that, before the step S1, a step S1A is further included, and the step S1A is: adding 5kg of TPEE, 0.8kg of toluene diisocyanate and 10kg of acetone into a reaction kettle, stirring for 2 hours at the stirring temperature of 60 ℃, filtering after stirring is finished, collecting solids, drying the solids in a 55 ℃ drying oven to obtain pretreated TPEE, and adding the pretreated TPEE into an internal mixer in the step S1.

Example 5

The present embodiment differs from embodiment 3 only in that, before the step S1, a step S1A is further included, and the step S1A is: adding 5kg of TPEE, 1kg of toluene diisocyanate and 15kg of acetone into a reaction kettle, stirring for 3 hours at the stirring temperature of 70 ℃, filtering after stirring, collecting solids, drying the solids in a 55 ℃ drying oven to obtain pretreated TPEE, and adding the pretreated TPEE into an internal mixer in the step S1.

Example 6

The present embodiment differs from embodiment 5 only in that, before the step S1, a step S1B is further included, and the step S1B is: adding 1.4kg of nano clay, 0.07kg of KH570 and 3.5kg of ethanol into a reaction bottle at room temperature, stirring for 1h, filtering after stirring, collecting solid, drying the solid in a 45 ℃ oven to obtain pretreated nano clay, and adding the pretreated nano clay into an internal mixer in the step S1.

Example 7

The present embodiment is different from embodiment 5 only in that before the step S1, a step S1B is further included, and the step S1B is: adding 1.4kg of nano clay, 0.11kg of KH570 and 4.9kg of ethanol into a reaction bottle at room temperature, stirring for 0.5h, filtering after stirring, collecting solid, drying the solid in an oven at 45 ℃ to obtain pretreated nano clay, and adding the pretreated nano clay into an internal mixer in the step S1.

Example 8

This example differs from example 7 only in that in step S1, 1.5kg of isopropyl palmitate was also added to the internal mixer for internal mixing.

Example 9

This example differs from example 7 only in that in step S1, 2.1kg of isopropyl palmitate was also added to the internal mixer for internal mixing.

Example 10

This example is different from example 9 only in that, in the step S1, the pretreated TPEE, the carbon fiber powder, the pretreated nanoclay, and isopropyl palmitate were previously added to a stirring barrel and stirred for 10min, mixed into a premix, and then charged into an internal mixer together with natural rubber and stearic acid.

Comparative example

Comparative example 1

This comparative example differs from example 3 only in that TPEE, carbon fiber powder and nanoclay are replaced with the same amount of natural rubber in the S1 step.

Comparative example 2

This comparative example differs from example 3 only in that in step S1, TPEE and carbon fiber powder are replaced with the same amount of natural rubber.

Comparative example 3

This comparative example differs from example 3 only in that in the S1 step, the same amount of natural rubber is used instead of TPEE.

Comparative example 4

This comparative example differs from example 3 only in that in the S1 step, the nanoclay is replaced with an equal amount of natural rubber.

Performance test

The shoe soles obtained in the examples and comparative examples of the present application were subjected to abrasion tests according to GB/T25262-2010 guide to abrasion test for vulcanized rubber or thermoplastic rubber, the test machine being an Akron abrasion tester, and the test results are shown in Table 2.

GB/T3903.6-2005 anti-slip performance of general test methods for footwear the soles obtained in the examples and comparative examples of the present application were tested for anti-slip, the test results are shown in Table 2.

TABLE 2

	Volume of abrasion (cm) ³ /1.61km)	Coefficient of friction
			Example 1	0.42	0.77
Example 2	0.45	0.79
			Example 3	0.43	0.79
Example 4	0.41	0.84
			Example 5	0.40	0.83
Example 6	0.34	0.85
			Example 7	0.35	0.83
Example 8	0.35	0.87
			Example 9	0.34	0.89
Example 10	0.30	0.95
			Comparative example 1	1.12	0.69
Comparative example 2	0.56	0.6
			Comparative example 3	0.54	0.61
Comparative example 4	0.95	0.75

As can be seen from Table 2, the wear volumes of examples 1-3 are all smaller than that of comparative example 1, and the friction coefficients are all larger than that of comparative example 1, which indicates that the wear resistance and the skid resistance of the boot sole can be improved by adding TPEE, carbon fiber powder and nano clay, probably because the lubricity of the carbon fiber powder is beneficial to winding the TPEE in the grids of natural rubber, the interaction force among molecular chain segments is improved, and the adhesive friction force between the boot sole and a contact surface is improved, so that the skid resistance of the boot sole is improved; the nano clay has a good reinforcing effect on natural rubber, improves the wear resistance of the boot sole, has good compatibility with TPEE, enables the nano clay to have good dispersibility and the boot sole to have good structural stability, and further improves and maintains the wear resistance of the boot sole.

The abrasion volume of the comparative example 2 is larger than that of the example 3, and the friction coefficient is smaller than that of the example 3, which shows that the addition of TPEE is beneficial to improving the anti-skid and wear-resisting properties of the boot sole, and the improvement range of the anti-skid property is larger; the abrasion volume and friction coefficient of comparative example 3 are similar to those of comparative example 2, indicating that the carbon fiber powder functions better when used in combination with TPEE.

Comparative example 4, which has a higher wear volume than example 3 and a similar coefficient of friction to example 3, shows that the addition of nanoclay helps to improve the wear resistance of the sole, while having less impact on the non-skid properties of the sole.

The abrasion volume of the embodiments 4 to 5 is similar to that of the embodiment 3, and the friction coefficient is greater than that of the embodiment 3, which shows that the antiskid performance of the boot sole can be better improved after the TPEE is pretreated by the toluene diisocyanate, probably because the toluene diisocyanate is combined with the active groups on the TPEE, the compatibility of the TPEE and the natural rubber is improved, the TPEE and the natural rubber are further wound, the interaction force between molecular chain segments is improved, and the antiskid performance of the boot sole is improved.

The abrasion volume of examples 6-7 is less than that of example 5 and the coefficient of friction is similar to that of example 5, indicating that the nano-clay after pretreatment with KH570 can better improve the wear resistance of the boot sole, probably because KH570 improves the dispersibility of nano-clay in natural rubber and helps to exert the reinforcing effect of nano-clay, thereby improving the wear resistance of the boot sole.

The abrasion volume of examples 8-9 is similar to that of example 7 and the coefficient of friction is greater than that of example 7, indicating that the addition of isopropyl palmitate can improve the non-skid properties of the boot sole, probably because isopropyl palmitate can improve the compatibility of the TPEE with the natural rubber, further promoting the wrapping of the TPEE with the natural rubber.

The abrasion volume of example 10 is less than that of example 9, and the friction coefficient is greater than that of example 9, which indicates that the formation of the premix first can improve the wear resistance and the skid resistance of the boot sole, probably because the pretreated nanoclay is mixed with isopropyl palmitate, so that the nanoclay is firstly dispersed in the isopropyl palmitate, and the subsequent dispersion of the nanoclay is promoted, thereby improving the wear resistance, and KH570 bound to the clay surface can be bound to the isopropyl palmitate and TPEE, thereby improving the binding strength of the isopropyl palmitate and TPEE, because the isopropyl palmitate can promote the TPEE to be wound with the natural rubber, and further the synergistic effect of the isopropyl palmitate and the nanoclay can improve the winding degree of the TPEE and the natural rubber, thereby further improving the skid resistance.

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

1. A preparation method of the antiskid wear-resistant boot is characterized by comprising the following steps:

s1, banburying natural rubber, TPEE, carbon fiber powder, nano clay and stearic acid for 10 to 15min, and then placing at room temperature for 18 to 24h to obtain master batch;

s4, bonding the boot bottom and the boot upper to obtain a boot;

in the S1 step, the banburying temperature is 100-110 ℃, and in the S2 step, the banburying temperature is 115-125 ℃;

s3, vulcanizing at the temperature of 130-150 ℃, for 8-12min and under the pressure of 20-25Mpa;

the weight ratio of the natural rubber, the TPEE, the carbon fiber powder, the nano clay, the stearic acid, the anti-aging agent, the accelerator and the sulfur is 100 (40) - (60): 4) - (7): 11) - (18): 0.5) - (0.8): 0.6) - (0.8): 1) - (1: 2;

before the step S1, the method also comprises a step S1A: TPEE, toluene diisocyanate and acetone are stirred for 2 to 3 hours at the temperature of 60 to 70 ℃, the weight ratio of the TPEE to the toluene diisocyanate to the acetone is 10 (1.6 to 2) (20 to 30), solid is obtained by filtering after stirring is finished, and the pretreated TPEE is obtained by drying.

2. The method for manufacturing a pair of anti-skid and wear-resistant boots as claimed in claim 1, wherein the method comprises the following steps: before the step S1, the method also comprises a step S1B: mixing and stirring the nano clay, the KH570 and the ethanol for 0.5 to 1h, wherein the weight ratio of the nano clay to the KH570 to the ethanol is 10 (0.5 to 0.8) to 25 to 35, filtering after stirring to obtain a solid, and drying to obtain the pretreated nano clay.

3. The method for manufacturing a pair of anti-slip and wear-resistant boots as claimed in claim 1, wherein the steps of: in the step S1, the banburying raw materials further comprise isopropyl palmitate, and the weight ratio of the natural rubber to the isopropyl palmitate is 100 (15 to 21).

4. The method for manufacturing a pair of anti-skid and wear-resistant boots as claimed in claim 3, wherein the steps of: in the step S1, TPEE, carbon fiber powder, nano clay and isopropyl palmitate are mixed into a premix in advance, and then the premix is banburied together with natural rubber and stearic acid.

5. The method for manufacturing a pair of anti-skid and wear-resistant boots as claimed in claim 1, wherein the method comprises the following steps: the anti-aging agent is DNP.

6. The method for manufacturing a pair of anti-slip and wear-resistant boots as claimed in claim 1, wherein the steps of: the accelerator is composed of an accelerator CZ and an accelerator DM, and the weight ratio of the accelerator CZ to the accelerator DM is 1 (0.5 to 1).