阅读说明：本技术 一种新型sebs接枝共聚物的制备方法 (Preparation method of novel SEBS (styrene-ethylene-butadiene-styrene) graft copolymer ) 是由 刘仁正 谢艳红 刘幸 刘亮 廖辉 于 2020-12-25 设计创作，主要内容包括：本申请涉及接枝共聚物领域,具体公开了一种新型SEBS接枝共聚物的制备方法。其制备方法包括以下步骤：称取所需原料,将SEBS和用于SEBS接枝GMA的引发剂加入溶剂中加热,搅拌混合后加入GMA、用于SEBS接枝GMA的润滑剂和用于SEBS接枝GMA的抗氧剂,继续搅拌混合,加热反应后得到混合物A；将混合物A和用于混合物A接枝TPU的引发剂加热,搅拌混合后加入TPU、用于混合物A接枝TPU的润滑剂和用于混合物A接枝TPU的抗氧剂,继续搅拌混合,加热反应后得到混合物B；将混合物B加入双螺杆挤出机中进行熔融共混挤出、冷却、造粒,经过过滤、提纯,得到GMA-SEBS-TPU成品。本申请制备的SEBS接枝共聚物可用作相容剂,其具有改善SEBS接枝共聚物支链不稳定,导致相容和增韧效果不佳的缺陷的优点。(The application relates to the field of graft copolymers, and particularly discloses a preparation method of a novel SEBS graft copolymer. The preparation method comprises the following steps: weighing required raw materials, adding SEBS and an initiator for SEBS grafted GMA into a solvent for heating, stirring and mixing, adding GMA, a lubricant for SEBS grafted GMA and an antioxidant for SEBS grafted GMA, continuously stirring and mixing, and heating for reaction to obtain a mixture A; heating the mixture A and an initiator for grafting the TPU to the mixture A, stirring and mixing, adding the TPU, a lubricant for grafting the TPU to the mixture A and an antioxidant for grafting the TPU to the mixture A, continuously stirring and mixing, and heating for reaction to obtain a mixture B; and adding the mixture B into a double-screw extruder for melt blending extrusion, cooling, granulating, filtering and purifying to obtain a GMA-SEBS-TPU finished product. The SEBS graft copolymer prepared by the method can be used as a compatilizer, and has the advantage of overcoming the defect that the branched chain of the SEBS graft copolymer is unstable, so that the compatibility and toughening effects are poor.)

1. A preparation method of a novel SEBS graft copolymer is characterized by comprising the following steps:

taking 180-mass parts of SEBS, 8-12-mass parts of TPU, 18-20-mass parts of GMA, 2-3.5-mass parts of initiator, 0.4-1.2-mass parts of lubricant and 0.8-1.8-mass parts of antioxidant as raw materials;

s1, weighing 1.2-2.2 parts by mass of an initiator for SEBS grafted GMA, 0.3-0.8 part by mass of a lubricant for SEBS grafted GMA and 0.5-1.1 part by mass of an antioxidant for SEBS grafted GMA;

adding SEBS and an initiator for SEBS grafted GMA into a solvent, heating to 70-85 ℃, stirring and mixing for 8-10min, adding GMA, a lubricant for SEBS grafted GMA and an antioxidant for SEBS grafted GMA, continuously stirring and mixing for 10-15min, heating to 80-120 ℃, and reacting for 3-6h to obtain a mixture A;

s2, weighing 0.8-1.3 parts by mass of an initiator for the mixture A to graft the TPU, 0.1-0.4 part by mass of a lubricant for the mixture A to graft the TPU, and 0.3-0.7 part by mass of an antioxidant for the mixture A to graft the TPU;

heating the mixture A and an initiator for grafting the TPU to the mixture A to 75-90 ℃, stirring and mixing for 6-8min, adding the TPU, a lubricant for grafting the TPU to the mixture A and an antioxidant for grafting the TPU to the mixture A, continuously stirring and mixing for 12-18min, heating to 90-140 ℃, and reacting for 2-5h to obtain a mixture B;

and S3, adding the mixture B into a double-screw extruder, performing melt blending extrusion, cooling, granulating, filtering and purifying to obtain a GMA-SEBS-TPU finished product.

2. The process for the preparation of a novel SEBS graft copolymer as claimed in claim 1, wherein: the mass ratio of the TPU to the GMA is 1 (1.8-2.2).

3. The process for the preparation of a novel SEBS graft copolymer as claimed in claim 2, wherein: the mass ratio of the TPU to the GMA is 1: 2.

4. The process for the preparation of a novel SEBS graft copolymer as claimed in claim 1, wherein: the mass ratio of the initiator to the SEBS is 1 (80-90).

5. The process for the preparation of the novel SEBS graft copolymer as claimed in claim 4, wherein: the mass ratio of the initiator to the SEBS is 1: 85.

6. The process for the preparation of a novel SEBS graft copolymer as claimed in claim 1, wherein: the initiator is di-tert-butyl peroxide.

7. The process for the preparation of a novel SEBS graft copolymer as claimed in claim 1, wherein: the lubricant is one or more of ethylene bis stearamide, solid paraffin and polyethylene wax.

8. The process for the preparation of a novel SEBS graft copolymer as claimed in claim 1, wherein: the antioxidant is one or more of antioxidant 1010, antioxidant 1035 and antioxidant 1076.

9. The process for the preparation of a novel SEBS graft copolymer as claimed in claim 1, wherein: the solvent is ethylbenzene or xylene.

10. The process for the preparation of a novel SEBS graft copolymer as claimed in claim 1, wherein: the rotating speed of the double-screw extruder is 190-250 r/min.

Technical Field

The application relates to the field of graft copolymers, in particular to a preparation method of a novel SEBS graft copolymer.

Background

Hydrogenated polystyrene-butadiene-styrene copolymer (SEBS) is a linear triblock copolymer having polystyrene as the terminal and an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as the middle elastomeric block. The SEBS is prepared by selectively hydrogenating unsaturated double bonds of polybutadiene at a rubber segment in SBS molecules, is a novel multipurpose thermoplastic elastomer, and has good stability and aging resistance because of no unsaturated double bonds.

SEBS has high elasticity of rubber at normal temperature, has fluidity of resin at high temperature, and is commonly used as a toughening agent of other polymer materials, particularly rubber materials due to excellent oxidation resistance, ultraviolet resistance, wear resistance and other properties. However, the molecular chain of SEBS does not contain polar groups or reactive groups, so that the SEBS has poor compatibility with polar materials, and when the SEBS is used as a toughening agent of the polar materials, the SEBS has poor modification effect, and a compatilizer is required to be added for blending modification.

In order to endow polarity to SEBS molecules, so that the SEBS molecules can be compatible with polar materials, and toughening modification is carried out on the polar materials, a common method at present is to carry out grafting modification on the SEBS. Wherein the most common monomer with grafting functional group is maleic anhydride, the SEBS, MAH and an initiator are uniformly mixed and then are mixed to obtain a grafting product, and the product SEBS-g-MAH is obtained after filtration and purification. However, the SEBS grafted maleic anhydride is unstable and easy to hydrolyze, thereby affecting the performance of the polymer material.

Disclosure of Invention

In order to overcome the defect that branched chains of SEBS (styrene-ethylene-butylene-styrene) graft copolymers are unstable, so that the compatibility and toughening effects are poor, the application provides a preparation method of a novel SEBS graft copolymer.

The preparation method of the novel SEBS graft copolymer adopts the following technical scheme:

a preparation method of a novel SEBS graft copolymer comprises the following steps:

taking 180-mass parts of SEBS, 8-12-mass parts of TPU, 18-20-mass parts of GMA, 2-3.5-mass parts of initiator, 0.4-1.2-mass parts of lubricant and 0.8-1.8-mass parts of antioxidant as raw materials;

s1, weighing 1.2-2.2 parts by mass of an initiator for SEBS grafted GMA, 0.3-0.8 part by mass of a lubricant for SEBS grafted GMA and 0.5-1.1 part by mass of an antioxidant for SEBS grafted GMA;

adding SEBS and an initiator for SEBS grafted GMA into a solvent, heating to 70-85 ℃, stirring and mixing for 8-10min, adding GMA, a lubricant for SEBS grafted GMA and an antioxidant for SEBS grafted GMA, continuously stirring and mixing for 10-15min, heating to 80-120 ℃, and reacting for 3-6h to obtain a mixture A;

s2, weighing 0.8-1.3 parts by mass of an initiator for the mixture A to graft the TPU, 0.1-0.4 part by mass of a lubricant for the mixture A to graft the TPU, and 0.3-0.7 part by mass of an antioxidant for the mixture A to graft the TPU; heating the mixture A and an initiator for grafting the TPU to the mixture A to 75-90 ℃, stirring and mixing for 6-8min, adding the TPU, a lubricant for grafting the TPU to the mixture A and an antioxidant for grafting the TPU to the mixture A, continuously stirring and mixing for 12-18min, heating to 90-140 ℃, and reacting for 2-5h to obtain a mixture B;

and S3, adding the mixture B into a double-screw extruder, performing melt blending extrusion, cooling, granulating, filtering and purifying to obtain a GMA-SEBS-TPU finished product.

By adopting the technical scheme, when the initiator and GMA are added into the SEBS, the free radical generated by the initiator abstracts hydrogen on a SEBS molecular chain to form a macromolecular free radical, so that a grafting reaction is initiated; the carbon-carbon double bond on the GMA molecular chain reacts with the macromolecular free radical in the grafting process, so that SEBS-g-GMA is generated, and the epoxy group on the GMA molecular chain has higher reactivity and can react with carboxyl, amino and other groups in the polar material, so that the reactive compatibilization effect is achieved;

when the initiator and the TPU are added into the SEBS, the free radicals generated by the initiator deprive hydrogen on the SEBS molecular chain to form macromolecular free radicals, so as to initiate grafting reaction; isocyanate groups on the molecular chain of the TPU react with macromolecular free radicals in the grafting process to generate SEBS-g-TPU, and hydroxyl groups and the isocyanate groups on the molecular chain of the TPU have higher reaction activity and can react with carboxyl, amino and other groups in a polar material to play a role in reactive compatibilization;

firstly, grafting SEBS and GMA, then grafting the obtained substance with TPU, grafting GMA firstly due to small steric hindrance generated by GMA, and facilitating the introduction of TPU, thereby improving the grafting rate and compatibility of SEBS graft copolymer, finally, melting, blending and extruding through a double-screw extruder, and purifying to obtain a finished product GMA-SEBS-TPU;

adding an initiator, GMA and TPU into SEBS, and grafting GMA and TPU on a SEBS main chain as branched chains respectively to generate GMA-SEBS-TPU, wherein on one hand, the grafting of GMA and TPU endows active groups such as epoxy groups, hydroxyl groups, isocyanate groups and the like to SEBS, so that polarity is provided for SEBS, the reactivity of SEBS is improved, and the synthesized SEBS graft has higher compatibility; on the other hand, GMA and TPU are not easy to hydrolyze as branched chains, and the synthesized SEBS graft can be used as a stable toughening agent and a compatilizer at the same time, so that a polar material is modified, and the defect that the branched chain of the SEBS graft copolymer is unstable, so that the compatibility and toughening effects are poor is overcome;

in addition, the introduction of the lubricant in the preparation process can reduce the viscosity of the melt and increase the flow speed of the melt, so that the SEBS can be grafted with GMA and TPU more easily to form a stable SEBS graft copolymer.

Preferably, the mass ratio of the TPU to the GMA is 1 (1.8-2.2).

By adopting the technical scheme, the monomer molecular chain of the TPU is longer than that of GMA, and the TPU molecule contains a benzene ring, so that the steric hindrance generated in the grafting process is large, the grafting rate can be influenced when the TPU content is too high, the compatibility of the SEBS graft copolymer is influenced, the resistance of the TPU and the GMA mixed according to the mass ratio in the grafting process is small, and the influence on the grafting rate is small.

Preferably, the mass ratio of the TPU to the GMA is 1: 2.

By adopting the technical scheme, under the condition that the contents of other raw materials and the preparation process are the same, the grafting effect of the TPU and GMA mixed according to the mass ratio on the SEBS is optimal, and the compatibility of the obtained SEBS graft copolymer is optimal.

Preferably, the mass ratio of the initiator to the SEBS is 1 (80-90).

By adopting the technical scheme, when the content of the initiator is less, the free radicals generated by the decomposition of the initiator are less, and the macromolecular free radicals formed by abstracting hydrogen on a macromolecular chain are correspondingly less, so that the grafting rate is lower; when the content of the initiator is higher, the free radicals generated by the decomposition of the initiator are excessive, so that side reaction between SEBS chains or GMA or TPU homopolymer is easily generated, the amount of the free radicals generated by the reaction of the initiator and the SEBS mixed according to the mass ratio is proper, and the grafting rate and the compatibility of the obtained SEBS graft copolymer are higher.

Preferably, the mass ratio of the initiator to the SEBS is 1: 85.

By adopting the technical scheme, under the condition that the contents of other raw materials and the preparation process are the same, the amount of the number of free radicals generated when the initiator mixed according to the mass ratio reacts with the SEBS is optimal, and the grafting rate and the compatibility of the obtained SEBS graft copolymer are optimal.

Preferably, the initiator is di-tert-butyl peroxide.

By adopting the technical scheme, the temperature of the SEBS, the TPU and the GMA is higher when the SEBS reacts with the TPU and the GMA, and the di-tert-butyl peroxide is an initiator which has higher activation energy and appropriate half-life at high temperature, so that the effect of initiating the grafting of the SEBS, the TPU and the GMA is the best.

Preferably, the lubricant is one or more of ethylene bis stearamide, paraffin wax and polyethylene wax.

By adopting the technical scheme, the ethylene bis stearamide, the solid paraffin and the polyethylene wax have the best lubricating effect on the SEBS, the GMA and the TPU, and the compatibility and the stability of the SEBS graft copolymer are improved conveniently.

Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 1035 and antioxidant 1076.

By adopting the technical scheme, the antioxidant 1010, the antioxidant 1035 and the antioxidant 1076 are all antioxidants which have strong stability and high solubility in SEBS.

Preferably, the solvent is ethylbenzene or xylene.

By adopting the technical scheme, the ethylbenzene and the xylene are both excellent organic solvents, and grafting of SEBS, GMA and TPU is facilitated.

Preferably, the rotating speed of the double-screw extruder is 190-250 r/min.

By adopting the technical scheme, the compatibility and the toughness of the SEBS graft copolymer obtained at the rotating speed are optimal.

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

1. according to the preparation method, the SEBS and the GMA are grafted firstly, then the obtained substance is grafted with the TPU, the GMA is grafted firstly due to small steric hindrance generated by the GMA, and the introduction of the TPU is facilitated, so that the grafting rate and the compatibility of the SEBS graft copolymer are improved, and finally the SEBS graft copolymer is melted, blended and extruded through a double-screw extruder, and the finished product GMA-SEBS-TPU is obtained after purification; adding an initiator, GMA and TPU into SEBS, and grafting GMA and TPU on a SEBS main chain respectively as branched chains to generate GMA-SEBS-TPU, wherein on one hand, the grafting of GMA and TPU endows active groups such as epoxy groups, hydroxyl groups, isocyanate groups and the like to SEBS, so that polarity is provided for SEBS, the reactivity of SEBS is improved, and the synthesized SEBS graft has higher compatibility; on the other hand, GMA and TPU are not easy to hydrolyze as branched chains, and the synthesized SEBS graft can be used as a stable toughening agent and a compatilizer simultaneously to modify polar materials, so that the defect that the branched chains of SEBS graft copolymers are unstable to cause poor compatibility and toughening effects is overcome.

2. Di-tert-butyl peroxide is preferably adopted as an initiator in the application, and the di-tert-butyl peroxide is an initiator with high activation energy at high temperature and appropriate half-life, so that the effect of initiating the grafting of SEBS, TPU and GMA is optimal, and the effect of improving the compatibility and stability of the SEBS graft copolymer is obtained.

3. In the application, one or more of ethylene bis stearamide, solid paraffin and polyethylene wax are preferably adopted as a lubricant, so that the lubricating effect on SEBS, GMA and TPU is optimal, and the compatibility and stability of the SEBS graft copolymer are improved conveniently.

Detailed Description

Source of raw materials

Unless otherwise specified, the specifications and sources of the raw materials in the following examples are shown in Table 1 below.

TABLE 1 raw material specifications and sources

Raw materials	Specification of	Source
			SEBS	KratonG1652	Shell company of America
TPU	1180A	Pasf, Germany
			GMA	H299431	SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.
Di-tert-butyl peroxide	B100924	SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.
			Ethylene bis stearamide	P02314	Shanghai Dingfen chemical science and technology Co., Ltd
Solid paraffin	P18384	Shanghai Dingfen chemical science and technology Co., Ltd
			Polyethylene wax	P34224	Shanghai Dingfen chemical science and technology Co., Ltd
Antioxidant 1010	S67391	SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd.
			Antioxidant 1035	S65385	SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd.
Antioxidant 1076	B65227	SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd.
			Cumene hydroperoxide	C109598	SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.
Pentaerythritol stearate	P299126	SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.
			Polyvinyl chloride	S51649	SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd.
Ethylbenzene production	E808935	SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd.
			Xylene	X112051	SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.

Examples

Example 1

Weighing 180g of SEBS, 8g of TPU, 18g of GMA, 2g of di-tert-butyl peroxide, 0.2g of ethylene bis stearamide, 0.1g of solid paraffin, 0.1g of polyethylene wax, 0.3g of antioxidant 1010, 0.4g of antioxidant 1035 and 0.1g of antioxidant 1076 as raw materials;

s1, weighing 1.2g of di-tert-butyl peroxide for SEBS grafted GMA, 0.1g of ethylene bis stearamide for SEBS grafted GMA, 0.1g of solid paraffin for SEBS grafted GMA, 0.1g of polyethylene wax for SEBS grafted GMA, 0.2g of antioxidant 1010 for SEBS grafted GMA and 0.3g of antioxidant 1035 for SEBS grafted GMA;

adding SEBS and di-tert-butyl peroxide for SEBS grafted GMA into an ethylbenzene solvent, heating to 85 ℃, stirring and mixing for 8min, adding GMA, ethylene bis stearamide for SEBS grafted GMA, solid paraffin for SEBS grafted GMA, polyethylene wax for SEBS grafted GMA, antioxidant 1010 for SEBS grafted GMA and antioxidant 1035 for SEBS grafted GMA, continuing stirring and mixing for 15min, heating to 120 ℃, and reacting for 3h to obtain a mixture A;

s2, weighing 0.8g of di-tert-butyl peroxide for the mixture A grafted TPU, 0.1g of ethylene bis stearamide for the mixture A grafted TPU, 0.1g of antioxidant 1010 for the mixture A grafted TPU, 0.1g of antioxidant 1035 for the mixture A grafted TPU and 0.1g of antioxidant 1076 for the mixture A grafted TPU;

heating the mixture A and di-tert-butyl peroxide used for grafting the TPU to the mixture A to 75 ℃, stirring and mixing for 6min, adding the TPU, the ethylene bis stearamide used for grafting the TPU to the mixture A, the antioxidant 1010 used for grafting the TPU to the mixture A, the antioxidant 1035 used for grafting the TPU to the mixture A and the antioxidant 1076 used for grafting the TPU to the mixture A, continuing stirring and mixing for 18min, heating to 140 ℃, and reacting for 2h to obtain a mixture B;

and S3, adding the mixture B into a double-screw extruder for melt blending extrusion, cooling and granulation, wherein the rotating speed of the double-screw extruder is 190r/min, and filtering and purifying to obtain a GMA-SEBS-TPU finished product.

Example 2

Weighing 200g of SEBS, 12g of TPU, 20g of GMA, 3.5g of di-tert-butyl peroxide, 0.3g of ethylene bis stearamide, 0.7g of solid paraffin, 0.2g of polyethylene wax, 0.5g of antioxidant 1010, 0.7g of antioxidant 1035 and 0.6g of antioxidant 1076 as raw materials;

s1, weighing 2.2g of di-tert-butyl peroxide for SEBS grafted GMA, 0.3g of ethylene bis stearamide for SEBS grafted GMA, 0.3g of solid paraffin for SEBS grafted GMA, 0.2g of polyethylene wax for SEBS grafted GMA, 0.3g of antioxidant 1010 for SEBS grafted GMA, 0.4g of antioxidant 1035 for SEBS grafted GMA and 0.4g of antioxidant 1076 for SEBS grafted GMA; adding SEBS and di-tert-butyl peroxide for SEBS grafted GMA into a xylene solvent, heating to 70 ℃, stirring and mixing for 10min, adding GMA, ethylene bis stearamide for SEBS grafted GMA, solid paraffin for SEBS grafted GMA, polyethylene wax for SEBS grafted GMA, antioxidant 1010 for SEBS grafted GMA, antioxidant 1035 for SEBS grafted GMA and antioxidant 1076 for SEBS grafted GMA, continuously stirring and mixing for 10min, heating to 80 ℃, and reacting for 6h to obtain a mixture A;

s2, weighing 1.3g of di-tert-butyl peroxide for the mixture A grafted TPU, 0.4g of paraffin wax for the mixture A grafted TPU, 0.2g of antioxidant 1010 for the mixture A grafted TPU, 0.3g of antioxidant 1035 for the mixture A grafted TPU and 0.2g of antioxidant 1076 for the mixture A grafted TPU; heating the mixture A and di-tert-butyl peroxide used for grafting the TPU to the mixture A to 90 ℃, stirring and mixing for 8min, adding the TPU, the paraffin wax used for grafting the TPU to the mixture A, the antioxidant 1010 used for grafting the TPU to the mixture A, the antioxidant 1035 used for grafting the TPU to the mixture A and the antioxidant 1076 used for grafting the TPU to the mixture A, continuing stirring and mixing for 12min, heating to 90 ℃, and reacting for 5h to obtain a mixture B;

and S3, adding the mixture B into a double-screw extruder, carrying out melt blending extrusion, cooling and granulation, wherein the rotating speed of the double-screw extruder is 250r/min, and filtering and purifying to obtain a GMA-SEBS-TPU finished product.

Example 3

176g of SEBS, 11g of TPU, 19.8g of GMA, 2.2g of di-tert-butyl peroxide, 0.3g of ethylene bis stearamide, 0.3g of solid paraffin, 0.2g of polyethylene wax, 0.3g of antioxidant 1010, 0.4g of antioxidant 1035 and 0.4g of antioxidant 1076 are weighed as raw materials;

s1, weighing 1.3g of di-tert-butyl peroxide for SEBS grafted GMA, 0.2g of ethylene bis stearamide for SEBS grafted GMA, 0.2g of solid paraffin for SEBS grafted GMA, 0.1g of polyethylene wax for SEBS grafted GMA, 0.2g of antioxidant 1010 for SEBS grafted GMA, 0.2g of antioxidant 1035 for SEBS grafted GMA and 0.3g of antioxidant 1076 for SEBS grafted GMA; adding SEBS and di-tert-butyl peroxide for SEBS grafted GMA into an ethylbenzene solvent, heating to 80 ℃, stirring and mixing for 9min, adding GMA, ethylene bis stearamide for SEBS grafted GMA, solid paraffin for SEBS grafted GMA, polyethylene wax for SEBS grafted GMA, antioxidant 1010 for SEBS grafted GMA, antioxidant 1035 for SEBS grafted GMA and antioxidant 1076 for SEBS grafted GMA, continuously stirring and mixing for 12min, heating to 90 ℃, and reacting for 4h to obtain a mixture A;

s2, weighing 0.9g of di-tert-butyl peroxide for the mixture A grafted TPU, 0.1g of ethylene bis stearamide for the mixture A grafted TPU, 0.1g of paraffin wax for the mixture A grafted TPU, 0.1g of polyethylene wax for the mixture A grafted TPU, 0.1g of antioxidant 1010 for the mixture A grafted TPU, 0.2g of antioxidant 1035 for the mixture A grafted TPU and 0.1g of antioxidant 1076 for the mixture A grafted TPU;

heating the mixture A and di-tert-butyl peroxide used for grafting the TPU with the mixture A to 85 ℃, stirring and mixing for 7min, adding the TPU, ethylene bis stearamide used for grafting the TPU with the mixture A, solid paraffin used for grafting the TPU with the mixture A, polyethylene wax used for grafting the TPU with the mixture A, antioxidant 1010 used for grafting the TPU with the mixture A, antioxidant 1035 used for grafting the TPU with the mixture A and antioxidant 1076 used for grafting the TPU with the mixture A, continuing stirring and mixing for 15min, heating to 120 ℃, and reacting for 3h to obtain a mixture B;

and S3, adding the mixture B into a double-screw extruder, carrying out melt blending extrusion, cooling and granulation, wherein the rotating speed of the double-screw extruder is 200r/min, and filtering and purifying to obtain a GMA-SEBS-TPU finished product.

Example 4

Weighing 189g of SEBS, 8.5g of TPU, 18.7g of GMA, 2.1g of di-tert-butyl peroxide, 0.2g of ethylene bis stearamide, 0.3g of solid paraffin, 0.5g of polyethylene wax, 0.3g of antioxidant 1010, 0.5g of antioxidant 1035 and 0.5g of antioxidant 1076 as raw materials;

s1, weighing 1.2g of di-tert-butyl peroxide for SEBS grafted GMA, 0.1g of ethylene bis stearamide for SEBS grafted GMA, 0.2g of solid paraffin for SEBS grafted GMA, 0.3g of polyethylene wax for SEBS grafted GMA, 0.2g of antioxidant 1010 for SEBS grafted GMA, 0.3g of antioxidant 1035 for SEBS grafted GMA and 0.3g of antioxidant 1076 for SEBS grafted GMA; adding SEBS and di-tert-butyl peroxide for SEBS grafted GMA into a xylene solvent, heating to 82 ℃, stirring and mixing for 10min, adding GMA, ethylene bis stearamide for SEBS grafted GMA, solid paraffin for SEBS grafted GMA, polyethylene wax for SEBS grafted GMA, antioxidant 1010 for SEBS grafted GMA, antioxidant 1035 for SEBS grafted GMA and antioxidant 1076 for SEBS grafted GMA, continuously stirring and mixing for 13min, heating to 100 ℃ and reacting for 5h to obtain a mixture A;

s2, weighing 0.9g of di-tert-butyl peroxide for the mixture A grafted TPU, 0.1g of ethylene bis stearamide for the mixture A grafted TPU, 0.1g of paraffin wax for the mixture A grafted TPU, 0.2g of polyethylene wax for the mixture A grafted TPU, 0.1g of antioxidant 1010 for the mixture A grafted TPU, 0.2g of antioxidant 1035 for the mixture A grafted TPU and 0.2g of antioxidant 1076 for the mixture A grafted TPU;

heating the mixture A and di-tert-butyl peroxide used for grafting the TPU with the mixture A to 80 ℃, stirring and mixing for 6min, adding the TPU, ethylene bis stearamide used for grafting the TPU with the mixture A, solid paraffin used for grafting the TPU with the mixture A, polyethylene wax used for grafting the TPU with the mixture A, antioxidant 1010 used for grafting the TPU with the mixture A, antioxidant 1035 used for grafting the TPU with the mixture A and antioxidant 1076 used for grafting the TPU with the mixture A, continuing stirring and mixing for 16min, heating to 130 ℃, and reacting for 4h to obtain a mixture B;

and S3, adding the mixture B into a double-screw extruder, carrying out melt blending extrusion, cooling and granulation, wherein the rotating speed of the double-screw extruder is 220r/min, and filtering and purifying to obtain a GMA-SEBS-TPU finished product.

Example 5

Weighing 187g of SEBS, 9.5g of TPU, 19g of GMA, 2.2g of di-tert-butyl peroxide, 0.2g of ethylene bis stearamide, 0.3g of solid paraffin, 0.4g of polyethylene wax, 0.3g of antioxidant 1010, 0.5g of antioxidant 1035 and 0.5g of antioxidant 1076 as raw materials;

s1, weighing 1.4g of di-tert-butyl peroxide for SEBS grafted GMA, 0.2g of ethylene bis stearamide for SEBS grafted GMA, 0.2g of solid paraffin for SEBS grafted GMA, 0.2g of polyethylene wax for SEBS grafted GMA, 0.2g of antioxidant 1010 for SEBS grafted GMA, 0.3g of antioxidant 1035 for SEBS grafted GMA and 0.3g of antioxidant 1076 for SEBS grafted GMA; adding SEBS and di-tert-butyl peroxide for SEBS grafted GMA into an ethylbenzene solvent, heating to 82 ℃, stirring and mixing for 9min, adding GMA, ethylene bis stearamide for SEBS grafted GMA, solid paraffin for SEBS grafted GMA, polyethylene wax for SEBS grafted GMA, antioxidant 1010 for SEBS grafted GMA, antioxidant 1035 for SEBS grafted GMA and antioxidant 1076 for SEBS grafted GMA, continuously stirring and mixing for 14min, heating to 100 ℃, and reacting for 5h to obtain a mixture A;

s2, weighing 0.8g of di-tert-butyl peroxide for the mixture A grafted TPU, 0.1g of paraffin wax for the mixture A grafted TPU, 0.2g of polyethylene wax for the mixture A grafted TPU, 0.1g of antioxidant 1010 for the mixture A grafted TPU, 0.2g of antioxidant 1035 for the mixture A grafted TPU and 0.2g of antioxidant 1076 for the mixture A grafted TPU;

heating the mixture A and di-tert-butyl peroxide used for grafting the TPU to the mixture A to 87 ℃, stirring and mixing for 6min, adding the TPU, the paraffin wax used for grafting the TPU to the mixture A, the polyethylene wax used for grafting the TPU to the mixture A, the antioxidant 1010 used for grafting the TPU to the mixture A, the antioxidant 1035 used for grafting the TPU to the mixture A and the antioxidant 1076 used for grafting the TPU to the mixture A, continuing stirring and mixing for 16min, heating to 130 ℃, and reacting for 4h to obtain a mixture B;

and S3, adding the mixture B into a double-screw extruder to perform melt blending extrusion, cooling and granulation, wherein the rotating speed of the double-screw extruder is 210r/min, and filtering and purifying to obtain a GMA-SEBS-TPU finished product.

Examples 6 to 7

Examples 6-7 differ from example 5 in the different ratios of di-tert-butyl peroxide to SEBS in the starting materials, as specified in the following table:

table 2 examples 6 to 7

Examples	Di-tert-butyl peroxide dosage/g	SEBS dosage/g
			Example 6	2	174
Example 7	2.3	188.6

Examples 8 to 9

Examples 8-9 differ from example 5 in the different proportions of GMA and TPU in the starting materials, as specified in the following table:

table 3 examples 8 to 9

Examples	GMA dosage/g	Amount of TPU used per g
			Example 8	19	10
Example 9	18.9	11

Example 10

Example 10 differs from example 5 in that the same mass of cumene hydroperoxide is used as initiator instead of di-tert-butyl peroxide.

Example 11

Example 11 differs from example 5 in that the same quality of pentaerythritol stearate was used as the lubricant.

Examples 12 to 13

Examples 12-13 differ from example 5 in the set rotational speed of the twin-screw extruder, as specified in the following table:

table 4 examples 12 to 13

Examples	Rotating speed/r.min of double-screw extruder-1
		Example 12	160
Example 13	270

Comparative example

Comparative example 1

Comparative example 1 is SEBS-g-MAH, available from Keteng, USA under the designation FG 1901.

Comparative example 2

Comparative example 2 is PE-g-MAH, available from Shanghai Dingfen chemical technology Co., Ltd., under the designation P35025.

Performance test

Detection method/test method

The examples and comparative examples were tested for their performance by the following test methods:

respectively weighing 20g of the compatilizer obtained in the examples 1-13 and the comparative examples 1-2, adding the compatilizer into 80g of polyvinyl chloride, stirring and mixing uniformly, adding the mixture into a double-screw extruder, and performing blending extrusion to obtain the composite material. The composite materials prepared in examples 1-13 are PVC/GMA-SEBS-TPU, the composite material prepared in comparative example 1 is PVC/SEBS-g-MAH, and the composite material prepared in comparative example 2 is PVC/PE-g-MAH.

The following tests were carried out on the composite materials prepared in the above steps, respectively:

1. testing the notch impact strength of the cantilever beam: the type A notch was produced by machining the specimen according to ISO2818:1994 using a pendulum impact tester model HIT25P from Zwick, Germany, tested in accordance with GB/T1843-2008.

2. Tensile yield stress and tensile strain at break test: the Young's modulus of the type Z005 from Zwick, Germany, was measured in accordance with GB/T1040.2-2006.

3. And (3) testing the bending strength: the test is carried out according to GB/T9341-2008 by adopting a Z020 type universal mechanical testing machine of Zwick company in Germany.

The results of examples 1-5 are reported in Table 5.

Table 5 examples 1-5 test results for properties

Example test items	Example 1	Example 2	Example 3	Example 4	Example 5
						Notched Izod impact Strength/kJ.m-2	16.3	16.7	17.4	17.2	18.1
Tensile yield stress/Mpa	57.1	56.8	57.4	57.5	58.7
						Tensile strain at break/%)	43	42	44	45	48
Flexural Strength/MPa	65.6	64.1	67.1	66.7	68.5

The results of examples 6-9 are reported in Table 6.

Table 6 results of performance tests of examples 6 to 9

Example test items	Example 6	Example 7	Example 8	Example 9
					Cantilever beamNotched impact strength/kJ · m-2	17.6	17.7	17.5	17.8
Tensile yield stress/Mpa	57.8	57.9	57.8	58.1
					Tensile strain at break/%)	46	45	47	46
Flexural Strength/MPa	67.3	67.4	67.1	67.6

The results of examples 10-13 are reported in Table 7.

TABLE 7 results of testing the properties of examples 10 to 13

The results of comparative examples 1-2 are reported in Table 8.

TABLE 8 results of testing the Performance of comparative examples 1-2

Comparative example test item	Comparative example 1	Comparative example 2
			Notched Izod impact Strength/kJ.m-2	12.3	13.7
Tensile yield stress/Mpa	37.1	39.8
			Tensile strain at break/%)	37	35
Flexural Strength/MPa	35.6	40.1

As can be seen by combining examples 1-4 and Table 5, examples 3 and 4 are superior to examples 1 and 2, so that when the mass ratio of TPU to GMA is 1 (1.8-2.2), the prepared SEBS graft copolymer has better toughness and compatibility; when the mass ratio of the di-tert-butyl peroxide to the SEBS is 1 (80-90), the prepared SEBS graft copolymer has better toughness and compatibility.

Combining examples 3-4 and 6-7 with tables 5-6, it can be seen that examples 6 and 7 are superior to examples 3 and 4, and thus the toughness and compatibility of the resulting SEBS graft copolymer is best when the mass ratio of TPU to GMA is 1: 2.

Combining examples 3-4 and examples 8-9 with tables 5-6, it can be seen that examples 8 and 9 are superior to examples 3 and 4, and thus the toughness and compatibility of the resulting SEBS graft copolymer are best when the mass ratio of di-tert-butyl peroxide to SEBS is 1: 85.

Combining examples 1-9 and tables 5-6, it can be seen that example 5 is the most preferred example, and therefore the most preferred embodiment is obtained when the mass ratio of TPU to GMA is 1:2 and the mass ratio of di-tert-butyl peroxide to SEBS is 1: 85.

Combining examples 5 and 10 and tables 5 and 7, it can be seen that the toughness and compatibility of the resulting SEBS graft copolymer are optimized when di-t-butyl peroxide is used as the initiator.

Combining examples 5 and 11 with tables 5 and 7, it can be seen that the toughness and compatibility of the resulting SEBS graft copolymer are best when one or more of ethylene bis stearamide, paraffin wax and polyethylene wax are used as a lubricant.

It can be seen by combining examples 5 and 12-13 with tables 5 and 7 that the toughness and compatibility of the SEBS graft copolymer obtained are best when the rotation speed of the twin-screw extruder is in the range of 190-250 r/min.

It can be seen by combining examples 1-13 and comparative examples 1-2 and combining tables 5-8 that the compatibility and toughening effect of GMA-SEBS-TPU is better than that of SEBS-g-MAH and PE-g-MAH when the GMA-SEBS-TPU is used as a compatilizer, which indicates that the GMA-SEBS-TPU improves the defect that the branched chain of SEBS graft copolymer is unstable and the compatibility and toughening effect is poor by introducing a polar group on SEBS.

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.