CN110818850A

CN110818850A - Compatilizer and synthetic method thereof, TPU (thermoplastic polyurethane) shoe material bottom material containing compatilizer and synthetic method thereof

Info

Publication number: CN110818850A
Application number: CN201911247918.5A
Authority: CN
Inventors: 王志民
Original assignee: Weihai Warner Plastic Co Ltd
Current assignee: Shandong Huana Plastic Group Co.,Ltd.
Priority date: 2019-12-06
Filing date: 2019-12-06
Publication date: 2020-02-21
Anticipated expiration: 2039-12-06
Also published as: CN110818850B

Abstract

A compatilizer and a synthetic method thereof, and a TPU (thermoplastic polyurethane) shoe material bottom material containing the compatilizer and a synthetic method thereof, wherein the compatilizer comprises the following raw materials in parts by weight: SEBS copolymer: 5-15 parts; naphthenic oil: 4-8 parts; prepolymer monomer: 0.5-1.5 parts; initiator: 0.1-0.5 part; the prepolymer monomer is composed of styrene, acrylic acid and butyl acrylate, the mass percentage of the styrene in the prepolymer monomer is not less than 15%, the mass percentage of the acrylic acid in the prepolymer monomer is not less than 10%, and the mass percentage of the butyl acrylate in the prepolymer monomer is not less than 40%. The compatilizer obtained under the condition that styrene, acrylic acid and butyl acrylate coexist can enable the TPU shoe material to have better physicochemical properties, supposedly because the reaction generated in the forming process forms a three-dimensional structure, the wear-resistant and slip-resistant performance of the TPU shoe material is further improved, and the extensibility is greatly improved.

Description

Compatilizer and synthetic method thereof, TPU (thermoplastic polyurethane) shoe material bottom material containing compatilizer and synthetic method thereof

Technical Field

The application relates to a compatilizer and a synthetic method thereof, and a TPU (thermoplastic polyurethane) shoe material primer containing the compatilizer and a synthetic method thereof.

Background

As is well known, the sole material has the characteristics of high elasticity, softness, wear resistance, oil resistance, hydrolysis resistance, wet and skid resistance, high and low temperature resistance and folding resistance, and meanwhile, the shoe material starts to move towards light weight, which is the basis of research and development of the product.

So far, shoe material bottom sheet materials mainly comprise two main varieties of rubber and TPU, and other materials also adopt foaming materials such as EVA, TPR, TPE, PVC and the like. The foaming materials are only used for shoe material midsoles and rarely used for bottom sheet materials due to poor weather resistance and aging resistance, and the shoe materials produced by the materials have poor elasticity and slip resistance, are easy to age and crack, and can only be used for producing low-end cheap shoes.

However, the disadvantages of TPU such as high hardness, poor wet skid resistance and high density also hinder their application. CN101824201A discloses a method for functionalizing SEBS, but when the obtained functionalized SEBS is used for modifying TPU, the effect of the modified TPU is not good, and on the basis, intensive research is carried out on how to obtain a proper compatilizer taking SEBS as a matrix.

Disclosure of Invention

In order to solve the above problems, the present application provides a compatibilizer, which comprises the following raw materials in parts by mass: SEBS copolymer: 5-15 parts; naphthenic oil: 4-8 parts; prepolymer monomer: 0.5-1.5 parts; initiator: 0.1-0.5 part; the prepolymer monomer is composed of styrene, acrylic acid and butyl acrylate, the mass percentage of the styrene in the prepolymer monomer is not less than 15%, the mass percentage of the acrylic acid in the prepolymer monomer is not less than 10%, and the mass percentage of the butyl acrylate in the prepolymer monomer is not less than 40%. The application adopts naphthenic oil as a medium, so that a prepolymer monomer can be grafted with SEBS copolymer well, a compatilizer obtained in the presence of styrene, acrylic acid and butyl acrylate is found in a test process, the TPU shoe material can have good physicochemical properties, and presumably a three-dimensional structure is formed due to reaction generated in a forming process, so that the wear-resistant and slip-resistant performance of the TPU shoe material is improved, and the extensibility is greatly improved.

Preferably, the mass ratio of the cycloalkanes in the naphthenic oil is not less than 95%. The naphthenic oil referred to herein may be 100% naphthenic hydrocarbon, and may be a naphthenic oil obtained by petroleum refining.

Preferably, the initiator is benzoyl peroxide or dicumyl peroxide.

Preferably, the composition also comprises an antioxidant: 0.05 to 0.2 portion.

On the other hand, the application also provides a preparation method of the compatilizer, which comprises the following steps: and blending the SEBS copolymer, naphthenic oil, a prepolymer monomer and an initiator, and granulating to obtain the compatilizer particles. Although better blending can be carried out in a very good mode and a better reaction effect is obtained, under the substances and the substance proportion, a compatilizer with better performance can be obtained by adopting a mode of granulating after blending, the compatilizer can play a better role in improving the TPU shoe material in the TPU shoe material, and the synthesis mode is simple and convenient.

Preferably, the blending time is not less than 20min, the granulation temperature is not lower than 200 ℃, and the die temperature is not lower than 180 ℃.

Preferably, the granulation is performed as follows: putting the raw materials into a double-screw extruder, and cutting by a water ring to obtain particles of the compatilizer.

On the other hand, the TPU shoe material containing the compatilizer is provided, and comprises the following raw materials in parts by mass: a compatilizer: 10-20 parts; TPU: 12-22 parts; rubber: 1-3 parts; initiator: 0.1 to 0.3 portion.

Preferably, the initiator is benzoyl peroxide.

On the other hand, the preparation method of the TPU shoe material comprises the following steps: and blending the compatilizer, the TPU, the rubber and the initiator, and then granulating to obtain the shoe material. The compatilizer is modified and used in the TPU containing rubber, so that the obtained shoe material has the advantages of good wear-resistant and slip-resistant performance, good flexibility and good aging resistance.

This application can bring following beneficial effect:

1. the application adopts naphthenic oil as a medium, so that a prepolymer monomer can be grafted with SEBS copolymer well, and a compatilizer obtained in the presence of styrene, acrylic acid and butyl acrylate is found in a test process, so that the TPU shoe material has good physical and chemical properties, supposedly because a reaction generated in a forming process forms a three-dimensional structure, the wear-resistant and slip-resistant performance of the TPU shoe material is improved, and the extensibility is greatly improved;

2. the compatilizer with better performance can be obtained by adopting a mode of granulating after blending, the compatilizer can play a better role in improving the TPU shoe material in the TPU shoe material, and the synthesis mode is simple and convenient;

3. the compatilizer is modified and used in the TPU containing rubber, so that the obtained shoe material has the advantages of good wear-resistant and slip-resistant performance, good flexibility and good aging resistance.

Detailed Description

In order to clearly illustrate the technical features of the present solution, the present application will be explained in detail through the following embodiments.

The compatibilizer obtained in the present application has its own use, i.e. for TPU shoe materials, and therefore the present application is characterized based on synthetic TPU shoe materials, but it should be noted that in this way, the effect of the compatibilizer on its physicochemical properties is its final purpose not because the compatibilizer is not a separate product but because the TPU shoe materials are used as end products.

The test procedure of the present application was performed as follows:

1 Synthesis of the Compatibilizing agent

S1, blending the raw material 1, wherein the components of the raw material 1 are shown in a table 1;

s2, putting the blended raw material 1 into a double-screw extruder, and performing water ring cutting at the granulation temperature of 200 ℃ and the die temperature of 180 ℃ to obtain the compatilizer particles.

Table 1:

2 preparing TPU shoe material by utilizing compatilizer

S3, blending the raw material 2, wherein the components of the raw material 2 are shown in a table 2;

s4, putting the blended raw material 2 into a double-screw extruder, and performing water ring cutting at the granulation temperature of 180 ℃ and the die temperature of 170 ℃ to obtain the TPU shoe material.

Table 2:

serial number	Compatibilizer number	Compatilizer (100g)	TPU(100g)	Rubber (100g)	Benzoyl peroxide (100g)
						1	1	10	12	1	0.1
2	2	15	17	2	0.2
						3	3	20	22	3	0.3
4	4	15	17	2	0.2
						5	5	15	17	2	0.2
6	6	15	17	2	0.2
						7	7	15	17	2	0.2
8	8	15	17	2	0.2
						9	9	15	17	2	0.2
10	10	15	17	2	0.2
						11	11	15	17	2	0.2
11	11	15	17	2	0.2

3 detection

The obtained TPU shoe material was tested for wear resistance, oil resistance and elongation at break, as shown in Table 3. Elongation is tested using SATRA TM137, wear resistance is tested using SATRA TM174, slip resistance is tested using ASTM F-609:

table 3:

it can be known from the above that when other substances such as the compatilizer number 5.6 are added, the corresponding shoe material number is also 5.6, the elongation at break is greatly reduced, presumably because only styrene, acrylic acid and butyl acrylate exist, the shoe material can form a net structure, so that the elongation at break is greatly improved, the side surface represents the flexibility of the shoe material, but when other substances exist, the occurrence of the net structure is prevented; when the content of styrene, acrylic acid and butyl acrylate added is not enough, shoe materials No. 7-12 are cross-compared, and the comparison shows that the lowest threshold value exists for the presence of styrene, acrylic acid and butyl acrylate, and when the threshold value is exceeded, the anti-slip performance is not changed greatly, but the wear resistance and the elongation at break have obvious deterioration tendency.

In conclusion, the compatilizer is synthesized by compounding the SEBS, the naphthenic oil, the styrene, the acrylic acid and the butyl acrylate, and the shoe material prepared from the compatilizer has the characteristics of high wear resistance, high flexibility and better slip resistance, so that the application space of the shoe material in the field is greatly improved, and the disadvantages caused by the TPU material are overcome.

The above are merely examples of the present application and are not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.

Claims

1. A compatibilizer, characterized by: the composite material comprises the following raw materials in parts by weight: SEBS copolymer: 5-15 parts; naphthenic oil: 4-8 parts; prepolymer monomer: 0.5-1.5 parts; initiator: 0.1-0.5 part; the prepolymer monomer is composed of styrene, acrylic acid and butyl acrylate, the mass percentage of the styrene in the prepolymer monomer is not less than 15%, the mass percentage of the acrylic acid in the prepolymer monomer is not less than 10%, and the mass percentage of the butyl acrylate in the prepolymer monomer is not less than 40%.

2. A compatibilizer according to claim 1 wherein: the mass ratio of the cycloalkanes in the naphthenic oil is not less than 95%.

3. A compatibilizer according to claim 1 wherein: the initiator is perhydrobenzoyl or dicumyl peroxide.

4. A compatibilizer according to claim 1 wherein: also comprises an antioxidant: 0.05 to 0.2 portion.

5. A process for preparing a compatibilizer as claimed in any one of claims 1 to 4, comprising: the method comprises the following steps: and blending the SEBS copolymer, naphthenic oil, a prepolymer monomer and an initiator, and granulating to obtain the compatilizer particles.

6. The method for preparing a compatibilizer according to claim 5, wherein: the blending time is not less than 20min, the granulation temperature is not lower than 200 ℃, and the neck mold temperature is not lower than 180 ℃.

7. The method for preparing a compatibilizer according to claim 5, wherein: the granulation is carried out in the following manner: putting the raw materials into a double-screw extruder, and cutting by a water ring to obtain particles of the compatilizer.

8. A TPU shoe material containing a compatilizer is characterized in that: the composite material comprises the following raw materials in parts by weight: a compatilizer: 10-20 parts; TPU: 12-22 parts; rubber: 1-3 parts; initiator: 0.1 to 0.3 portion.

9. The method for preparing TPU shoe material according to claim 8, characterized in that: the initiator is perhydrobenzoyl.

10. A process for the preparation of TPU shoe material as claimed in any one of claims 8 to 9 wherein: the method comprises the following steps: and blending the compatilizer, the TPU, the rubber and the initiator, and then granulating to obtain the shoe material.