CN112300525A

CN112300525A - graphene/SEBS composite material with high strength and high damping characteristic and preparation method thereof

Info

Publication number: CN112300525A
Application number: CN202011165737.0A
Authority: CN
Inventors: 曾尤; 张藤心; 王函; 张建岗; 郝亚斌; 孙新阳
Original assignee: Institute of Metal Research of CAS
Current assignee: Institute of Metal Research of CAS
Priority date: 2020-10-27
Filing date: 2020-10-27
Publication date: 2021-02-02
Anticipated expiration: 2040-10-27
Also published as: CN112300525B

Abstract

The invention relates to the field of nano-carbon composite materials, in particular to a graphene/SEBS composite material with high strength and high damping characteristics and a preparation method thereof. Firstly, modifying multiple hydrogen bond molecules on the surface of graphene to obtain graphene nanofiller grafted by the multiple hydrogen bond molecules; introducing the multiple hydrogen bond molecules into SEBS molecular chain segments through a grafting reaction to obtain SEBS grafted by the multiple hydrogen bond molecules; and finally, mixing the graphene grafted by the multiple hydrogen bond molecules and the SEBS in an organic solvent system by a solution blending method, uniformly stirring, removing the solvent, and performing hot press molding to obtain the graphene/SEBS composite material. The interface of each component in the composite material forms a hydrogen bond network, the graphene nano filler and the hydrogen bond network play a role in a synergistic manner, the mechanical property of the SEBS matrix is obviously enhanced, the viscoelastic damping property of the composite material is also obviously improved, and the composite material has an important application prospect in the field of high-performance damping engineering materials.

Description

graphene/SEBS composite material with high strength and high damping characteristic and preparation method thereof

Technical Field

The invention relates to the field of nano-carbon composite materials, in particular to a graphene/SEBS composite material with high strength and high damping characteristics and a preparation method thereof.

Background

SEBS is a linear triblock copolymer with polystyrene as a terminal segment and an ethylene-butylene copolymer obtained by hydrogenation of polybutadiene as a middle segment. The SEBS is a novel elastomer similar to rubber, not only has the excellent characteristics of a thermoplastic elastomer, but also does not need to be vulcanized like rubber in the forming process, and has been widely applied and paid much attention in many fields such as sports goods, automobile materials, household appliances, building industry and the like. At present, with the high efficiency, rapidity and automation of machine equipment, the problems of resonance, noise and material fatigue caused by mechanical vibration become important problems to be solved urgently, and the preparation of the SEBS material with the high damping and vibration reduction characteristics has important use value and practical significance. The rubber elastomer material generates high energy dissipation through the friction motion of a molecular chain under the action of an external load due to the unique viscoelastic property. However, it is worth noting that the frictional motion of the molecular chains, which contributes to the damping performance, inevitably causes the mechanical properties (such as strength and modulus) of the polymer to be reduced. The key point of preparing the SEBS with high damping characteristic is to simultaneously improve the mechanical strength and the damping loss value of the material.

At present, the method capable of effectively improving the damping loss of the polymer without sacrificing the strength and the modulus is to introduce the nano-filler into the polymer. Compared with traditional fillers such as montmorillonite, graphite, mica sheet, graphite alkene is as novel nanometer charcoal material, micro-nano scale has, unique two-dimensional structure, excellent mechanical properties (elastic modulus is up to 1TPa), super large specific surface area, can effectively strengthen the mechanical strength of polymer under few addition, and the unique two-dimensional nanometer lamellar structure of graphite alkene can introduce more abundant interface in combined material, and can increase the shear deformation of near lamella polymer, make combined material produce more energy dissipation at deformation in-process, help promoting the viscoelastic damping performance of material, the preparation and the development that have opened up important thinking for high performance damping material. However, the effective reinforcement of the graphene nanofiller to the matrix is limited by the dispersion of the graphene and the interfacial interactions. The graphene and SEBS elastic matrixes which do not contain polar functional groups have poor interface compatibility, the dispersibility of the graphene can be improved to a certain extent by carrying out chemical modification such as oxidation and coupling agent modification on the graphene, but the interface bonding force between the graphene and a polymer matrix is difficult to effectively improve and regulate, so that the graphene cannot effectively exert excellent mechanical properties and unique structural characteristics, and the high strength and high damping property of the graphene/polymer composite material and the application of the graphene/polymer composite material in the damping field are greatly limited. How to regulate and design the interface combination between the graphene and the polymer is a key problem for obtaining the graphene/SEBS composite material with high strength and high damping characteristics.

Disclosure of Invention

The invention aims to provide a graphene/SEBS composite material with high strength and high damping characteristics and a preparation method thereof. The reinforcing effect and the interface slippage energy dissipation mechanism of the graphene nano filler are cooperated with the dynamic fracture/generation energy dissipation mechanism of a hydrogen bond network, so that the problem that the high strength and the high damping loss of the existing rubber polymer material are difficult to obtain at the same time is solved.

The technical scheme of the invention is as follows:

the graphene/SEBS composite material with the characteristics of high strength and high damping comprises, by weight, 100 parts of SEBS grafted by multiple hydrogen bond molecules and 0.1-2 parts of graphene grafted by the multiple hydrogen bond molecules.

The graphene/SEBS composite material with high strength and high damping characteristic uses multiple hydrogen bond molecules as follows: the multi-hydrogen-bond molecular hydrogen-bonding agent comprises 3-amino-1, 2,4 triazole, 2-aminopyridine, 2, 6-diaminopyridine or 2, 4-diamino-1, 3, 5-triazine, a hydrogen bond donor and an acceptor are contained in the multi-hydrogen-bond molecule, the donor and the acceptor of the multi-hydrogen-bond molecule can be associated to form a multi-hydrogen-bond network, and the multi-hydrogen-bond molecule contains a reactive amino functional group.

According to the graphene/SEBS composite material with high strength and high damping characteristics, a precursor of the SEBS grafted by multiple hydrogen bond molecules is the SEBS grafted by maleic anhydride, wherein the grafting rate of maleic anhydride functional groups is 0.5-2.5%.

The graphene/SEBS composite material with high strength and high damping characteristic adopts graphene oxide grafted by multiple hydrogen bond molecules, wherein the graphene oxide is prepared by a chemical oxidation method or an electrolytic oxidation ink method, the atomic percent of oxygen elements is 30% -60%, the types of oxygen groups are carboxyl, epoxy, hydroxyl and carbonyl, the diameter of a lamella is 100 nm-10 mu m, and the number of the lamella layers is 1-2.

The graphene/SEBS composite material with high strength and high damping characteristic is prepared from multiple hydrogen bond molecule grafted graphene, wherein the atomic percentage of nitrogen is 3% -15%, the atomic percentage of oxygen is 5% -30%, and the diameter of a sheet layer is 100 nm-10 mu m.

The preparation method of the graphene/SEBS composite material with high strength and high damping characteristics comprises the following steps:

(1) taking Graphene Oxide (GO) as a raw material, adding multiple hydrogen bond molecules and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) into a GO aqueous dispersion, ultrasonically dispersing for 0.5-1 h, and stirring for reacting for 4-12 h to obtain GO modified by the multiple hydrogen bond molecules; adding vitamin C, stirring and reacting for 10-24 h, performing suction filtration and cleaning on a product, and drying to obtain the graphene modified by multiple hydrogen bond molecules;

(2) using SEBS as a raw material, and grafting Maleic Anhydride (MAH) to SEBS molecular chain segments by a solution method or a melt blending method to obtain MAH grafted SEBS (MAH-SEBS); using MAH-SEBS as a precursor, and grafting and modifying multiple hydrogen bond molecules to SEBS molecular chain segments by a solution method or a melt blending method to obtain the SEBS grafted with the multiple hydrogen bond molecules;

(3) ultrasonically dispersing graphene grafted by multiple hydrogen bond molecules in N, N-Dimethylformamide (DMF), dissolving SEBS grafted by multiple hydrogen bond molecules in dimethylbenzene, mixing the two, ultrasonically dispersing for 0.5-2 h until the graphene is uniformly dispersed in an organic solvent system, and stirring for 1-3 h at the temperature of 60-80 ℃; and pouring the mixed solution into ethanol for precipitation, performing suction filtration to separate a product, drying, and performing hot press molding to finally obtain the graphene/SEBS composite material.

In the preparation method of the high-strength high-damping graphene/SEBS composite material, in the step (1), the concentration of the GO water dispersion is 0.05-3 mg/ml, and the stirring reaction conditions for obtaining the GO modified by multiple hydrogen bond molecules are as follows: stirring for 3-8 h at normal temperature and stirring for 1-4 h in oil bath at 70-95 ℃; the mass ratio of GO to vitamin C is 1: 2-1: 10, and after the vitamin C is added, the stirring reaction temperature is 25-70 ℃.

In the step (2), the preparation method of the graphene/SEBS composite material with high strength and high damping characteristics comprises the steps of dissolving SEBS and MAH in a xylene or toluene solvent, dripping dicumyl peroxide (DCP), and carrying out reflux stirring reaction at 120-140 ℃ for 3-8 hours; the process for preparing the maleic anhydride grafted SEBS by the melt blending method comprises the steps of mixing the SEBS, the MAH and the DCP uniformly in advance, adding the mixture into an internal mixer, internally mixing the mixture for 5-20 min at the temperature of 140-170 ℃, and dissolving the obtained product by using xylene; in the solution method or the melt blending method, the concentration of SEBS is 0.2-2 g/mL, the mass of MAH is 5-20 wt% of the mass of SEBS, and the mass of DCP is 1-10 wt% of the mass of SEBS; and after the reaction is finished, pouring the reaction solution into ethanol, acetonitrile or acetone, filtering, cleaning and drying the precipitate to obtain the MAH-SEBS.

In the step (2), the solution method for preparing the SEBS grafted with the multiple hydrogen bond molecules comprises the steps of dissolving the MAH-SEBS in xylene, dispersing the multiple hydrogen bond molecules in DMF, mixing the MAH-SEBS and the DMF, and stirring at 60-90 ℃ for 0.5-5 h to obtain a product; the preparation method of the SEBS grafted by the multiple hydrogen bond molecules by the melt blending method comprises the steps of adding the MAH-SEBS and the multiple hydrogen bond molecules into an internal mixer, and internally mixing for 8-20 min at 60-90 ℃ to obtain a product; in the solution method or the melt blending method, the volume ratio of DMF to xylene is 1 (30-60), and the molar ratio of multiple hydrogen bond molecules to MAH grafted on SEBS is 1 (1-3).

The preparation method of the graphene/SEBS composite material with the high strength and the high damping characteristic comprises the step (3), wherein the volume ratio of DMF to xylene in an organic solvent system is 1 (4-6), the hot press forming temperature is 150-170 ℃, the hot press forming time is 15-30 min, and the pressure maintaining time is 1-3 h.

The design idea of the invention is as follows:

due to poor interface compatibility of the traditional graphene/SEBS composite material, the graphene is difficult to effectively exert excellent mechanical properties and unique structural characteristics in the graphene, the mechanical strength and the damping property of the composite material are restricted, and the high-strength high-damping property of the graphene/polymer composite material and the application of the graphene/SEBS composite material in the damping field are greatly limited. In order to regulate and design the interface combination between graphene and a polymer so as to obtain the graphene/SEBS composite material with high strength and high damping characteristics, the same multiple hydrogen bond molecules are respectively grafted on the molecular chains of graphene and SEBS by a chemical method, and then the graphene and the SEBS are blended by a solution method to prepare the composite material. Hydrogen bond association among multiple hydrogen bond molecules constructs hydrogen bond network interfaces among components in the composite material, a solution blending method ensures uniform dispersion of graphene in an SEBS matrix, the finally obtained composite material is an elastomer containing nano graphene filler and multiple hydrogen bond networks, and hydrogen bond network effects are formed among graphene and graphene sheet layers, between graphene and a molecular chain of the matrix and among matrix molecular chain interfaces. The existence of hydrogen bonds at the interface is beneficial to the mechanical load transfer between the graphene and the SEBS, and the effective mechanical enhancement of the graphene to the SEBS material is realized; the hydrogen bond is used as a reversible sacrificial bond, so that energy can be continuously consumed by continuously generating and consuming energy when the graphene sheet layer generates interface slip to dissipate energy, and the energy dissipation of the material is greatly improved, so that the high-strength and high-damping characteristics of the graphene/SEBS composite material are realized.

The method is remarkably different from the traditional design idea of introducing hindered phenol micromolecules or modified polymer chains to obtain a hydrogen bond network, and the hydrogen bond molecule modified graphene nano filler with excellent mechanical property and high stability is used for replacing micromolecule additives with poor stability and easy precipitation. In addition, in the mechanism of mechanical enhancement and damping improvement, in addition to the utilization of a hydrogen bond network among polymer molecular chains to improve the mechanical strength and energy dissipation of a polymer matrix, the enhancement effect of the graphene nanofiller, the energy consumption mechanism of nanosheet layer interface slippage and the energy consumption mechanism of interface hydrogen bond dynamic fracture/generation are introduced, so that the improvement of the strength and damping performance of the composite material is more remarkable. According to the invention, hydrogen bond networks are formed at the interfaces of all components in the composite material, and the graphene nano filler and the hydrogen bond networks play a role in a synergistic manner, so that the mechanical property of the SEBS matrix is obviously enhanced, and the viscoelastic damping property of the composite material is also obviously improved.

The invention has the advantages and beneficial effects that:

1. according to the preparation method, graphene oxide is used as a raw material, multiple hydrogen bond molecules are grafted and modified, and the situation that an irreversible strong covalent bond is formed between an oxygen group of the graphene oxide and a polymer matrix, so that the strength of the composite material is improved and the damping is reduced is avoided; the multiple hydrogen bond network bonds formed by the graphene and the polymer matrix are high in energy and have reversible characteristics of fracture regeneration, so that the strength of the composite material and the energy dissipation at the interface can be improved simultaneously.

2. According to the invention, graphene grafted by multiple hydrogen bond molecules is used as an additive of a polymer, compared with the traditional inorganic filler in the damping field, the emerging nano carbon material graphene has more excellent modulus and super large specific surface area, can effectively enhance the mechanical strength of the polymer under the condition of a very small addition amount, and introduces rich interfaces; in addition, multiple hydrogen bond molecular grafting of the graphene sheet layer can form a strong hydrogen bond effect with a polymer matrix, and a traditional small molecular substance which is poor in stability and easy to separate out does not need to be introduced into a composite material system to provide the hydrogen bond effect, so that the strength and the damping performance of the composite material are improved, and the stability of the composite material is maintained.

3. According to the invention, the mechanical strength and viscoelastic damping performance of the composite material can be effectively adjusted by quantitatively controlling the addition amount of the graphene modified by multiple hydrogen bond molecules, the lamellar particle size of the graphene oxide, the oxygen group content on the surface of the graphene oxide and the grafting rate of MAH on a polymer molecular chain, and the composite material has an important application prospect in the field of high-performance damping engineering materials.

4. The method not only utilizes the bonding energy and the dynamic reversible fracture/regeneration characteristic of multiple hydrogen bond networks among polymer molecular chains, but also fully utilizes the lamellar structure characteristic and the excellent mechanical property of the graphene, combines the reinforcing effect of the graphene nano filler, the energy consumption mechanism of the interface slippage of the nanosheet layer and the energy consumption mechanism of the dynamic fracture/generation of the interface hydrogen bonds, has more remarkable enhancing effect on the strength and the damping performance of the composite material, and provides a new idea for the design of the high-performance damping material.

Drawings

Fig. 1 is a stress-strain curve (a) of the graphene/SEBS composite prepared in example 1 and an SEBS matrix and a comparison (b) of tensile modulus and hysteresis loss thereof. (a) In the figure, the abscissa Strain represents Strain (%), and the ordinate Stress represents Stress (MPa); (b) in the figure, the left ordinate Tensile modulus represents Tensile modulus (MPa), and the right ordinate hystersis loss represents Hysteresis loss (MJ m)^-3)。

Fig. 2 shows the dynamic thermo-mechanical properties of the graphene/SEBS composite material and the SEBS matrix prepared in example 1, which sequentially include a change (a) of storage modulus with temperature, a change (b) of loss modulus with temperature, and a change (c) of loss factor with temperature from left to right. (a) In the figure, the abscissa Temperature represents Temperature (. degree. C.) and the ordinate Storage modulus represents Storage modulus (MPa); (b) in the figure, the abscissa Temperature represents Temperature (. degree. C.) and the ordinate Loss modulus represents Loss modulus (MPa); (c) in the figure, the abscissa A represents the temperature (. degree. C.) and the ordinate Tan delta represents the loss factor.

Detailed Description

To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are given in the accompanying drawings. The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the specific implementation process, the high-strength high-damping graphene/SEBS composite material and the preparation method thereof are as follows:

the graphene/SEBS composite material with the high strength and the high damping characteristic comprises, by weight, 100 parts of SEBS grafted by multiple hydrogen bond molecules and 0.1-2 parts (preferably 0.2-1 part) of graphene grafted by multiple hydrogen bond molecules. Among these, multiple hydrogen bonding molecules are used, such as: 3-amino-1, 2,4 triazole, 2-aminopyridine, 2, 6-diaminopyridine, 2, 4-diamino-1, 3, 5-triazine, etc., wherein the multiple hydrogen bond molecule comprises a hydrogen bond donor and an acceptor, the donor and the acceptor of the multiple hydrogen bond molecule can form a dimer through double, triple or quadruple hydrogen bonds, and the multiple hydrogen bond molecule contains a reactive amino functional group. The precursor of the SEBS grafted by multiple hydrogen bond molecules is SEBS grafted by maleic anhydride, wherein the grafting rate of maleic anhydride functional groups is 0.5-2.5%. The multiple hydrogen bond molecule grafted graphene is prepared from graphene oxide by a chemical oxidation method or an electrolytic oxidation graphite method, wherein the atomic percentage of oxygen elements is 30-60%, the types of oxygen groups comprise carboxyl, epoxy, hydroxyl or carbonyl, the diameter of a lamella is 100 nm-10 mu m, and the number of the lamella layers is 1-2. The atomic percentage of nitrogen element of the graphene grafted by multiple hydrogen bond molecules is 3-15%, the atomic percentage of oxygen element is 5-30%, and the diameter of a sheet layer is 100 nm-10 μm.

1. preparation of multiple hydrogen bond molecule modified graphene

Graphene Oxide (GO) is used as a raw material, GO is dispersed in water to prepare 0.05-3 mg/ml of GO aqueous dispersion, multiple hydrogen bond molecules and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) are added, ultrasonic dispersion is carried out for 0.5-1 h, stirring is carried out for 3-8 h at normal temperature and stirring is carried out for 1-4 h in an oil bath at 70-95 ℃, and GO modified by the multiple hydrogen bond molecules is obtained; and adding vitamin C, wherein the mass of the vitamin C is 3-10 times that of GO, stirring and reacting for 10-24 hours at 25-70 ℃, performing suction filtration and cleaning on a product, and drying to obtain the graphene modified by multiple hydrogen bond molecules.

For the sake of illustration, taking the typical triple hydrogen bonding molecule 3-amino-1, 2,4 triazole (ATA) as an example, the main reaction equations involved in the process are listed as follows:

2. preparation of SEBS modified by multiple hydrogen bond molecules

Using SEBS as a raw material, and grafting Maleic Anhydride (MAH) to SEBS molecular chain segments by a solution method or a melt blending method to obtain MAH grafted SEBS (MAH-SEBS); the preparation method comprises the following steps of dissolving SEBS and MAH in a xylene solvent, heating to dissolve the SEBS and the MAH, slowly dropping dicumyl peroxide (DCP), and carrying out reflux stirring reaction at 120-140 ℃ for 3-8 hours; the process of preparing the maleic anhydride grafted SEBS by the melt blending method comprises the steps of mixing the SEBS, the MAH and the DCP uniformly in advance, adding the mixture into an internal mixer, internally mixing the mixture for 5-20 min at the temperature of 140-170 ℃, and dissolving the product by using xylene. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol, acetonitrile or acetone, filtering to obtain a precipitate, and cleaning and drying to obtain the MAH-SEBS.

The main reaction equations involved in the process are listed below:

in the solution method and the melt blending method, the concentration of SEBS in dimethylbenzene is 0.2-2 g/mL, the mass of MAH is 5-20 wt% of the mass of SEBS, and the mass of DCP is 0.5-8 wt% of the mass of SEBS.

MAH-SEBS is used as a raw material, multiple hydrogen bond molecules are grafted and modified to SEBS molecular chain segments through a solution method or a melt blending method, and the SEBS grafted with the multiple hydrogen bond molecules is obtained. The process for preparing the SEBS grafted by the multiple hydrogen bond molecules by the solution method comprises the following steps: dissolving the MAH-SEBS in xylene, dispersing multiple hydrogen bond molecules in N, N-Dimethylformamide (DMF), mixing the MAH-SEBS and the DMF, and stirring at 60-90 ℃ for 0.5-5 h to obtain a product; the process for preparing the SEBS grafted by the multiple hydrogen bond molecules by the melt blending method comprises the following steps: and adding the MAH-SEBS and the multiple hydrogen bond molecules into an internal mixer, and internally mixing for 8-20 min at 60-90 ℃ to obtain the product.

in the solution method and the melt blending method, the volume ratio of DMF to xylene is 1 (30-60), and the molar ratio of hydrogen bond molecules to grafted MAH is 1 (1-3).

3. Preparation of graphene/SBES composite material

Ultrasonically dispersing graphene grafted by hydrogen bond molecules in DMF (dimethyl formamide), dissolving SEBS grafted by hydrogen bond molecules in xylene, mixing the two, ultrasonically dispersing for 0.5-2 h until the graphene is uniformly dispersed in an organic solvent system, and stirring and mixing for 1-3 h at 60-80 ℃. And pouring the reaction liquid into excessive ethanol for precipitation, performing suction filtration, drying the residual solvent, performing hot pressing at 150-170 ℃ for 15-30 min, and maintaining the pressure for 1-3 h for molding to finally obtain the graphene/SEBS composite material.

The obtained graphene/SEBS composite material is an elastomer containing nano-graphene and multiple hydrogen bond networks, the graphene is uniformly dispersed in the elastomer, and hydrogen bond actions formed by multiple hydrogen bond molecules are respectively formed between graphene sheet layers, between graphene sheet layers and a molecular chain of a matrix and between molecular chains of the matrix.

For ease of illustration, a typical triple hydrogen bonding molecule, 3-amino-1, 2,4 triazole (ATA), is exemplified by the following:

the present invention will be described in further detail below with reference to examples.

Example 1

In this embodiment, the preparation method of the graphene/SEBS composite material with high strength and high damping characteristics is as follows:

1. preparing 100mL of 2mg/mL GO/water dispersion prepared by an electrolytic oxidation graphite method, wherein the atomic ratio of oxygen elements of GO is 36%, the GO lamellar contains carboxyl, epoxy, hydroxyl and carbonyl functional groups, the diameter of the lamellar is 100 nm-3 mu m, the number of lamellar layers is a single layer, weighing 2g of EDC and 0.3g of ATA, adding into the GO water dispersion, and ultrasonically dispersing for 0.5 h. And placing the ultrasonic dispersion liquid into a conical flask, stirring and reacting under a constant-temperature digital display magnetic stirrer, stirring at normal temperature for 6 hours, and then stirring and reacting under an oil bath at 90 ℃ for 2.5 hours.

2. After the reaction is finished, adding 1g of vitamin C into the reaction solution, continuously stirring and reacting for 24h at 50 ℃, filtering the reaction product by using an aqueous filter membrane, repeatedly washing for three times, and freeze-drying to obtain the ATA grafted graphene, wherein the atomic percent of nitrogen element is 4.78%, the atomic percent of oxygen element is 13.56%, and the diameter of a lamella is 100 nm-3 mu m.

3. 60g of SEBS and 12g of maleic anhydride are weighed and added into a three-necked flask containing 145mL of xylene, and the mixture is placed in an oil bath at the temperature of 80 ℃ and stirred electrically until the mixture is completely dissolved. Then the temperature is raised to 130 ℃, 5g of DCP is added drop by drop, and the reflux reaction is carried out for 4 hours. After the reaction is finished, pouring the reaction liquid into excessive ethanol, precipitating a product MAH-SEBS, removing unreacted MAH and DCP, repeatedly washing the product for three times, and drying in vacuum at 60 ℃.

4. And calibrating the grafting rate of the MAH in the MAH-SEBS to be 1.70 percent by taking 0.1mol/L KOH ethanol solution and 0.1mol/L HCl-isopropanol solution as titration standard samples.

5. Weighing the 5g of MAH-SEBS in a beaker filled with 50mL of dimethylbenzene, and placing the beaker in an oil bath at 60 ℃ until the MAH-SEBS is completely dissolved; 0.073g of ATA is weighed and ultrasonically dispersed in 2mL of DMF, and then the mixture is added into a xylene solution of MAH-SEBS and placed in an oil bath at 60 ℃ to be stirred and react for 1h, so as to obtain a solution of ATA grafted SEBS.

6. Weighing 37.5mg of ATA grafted graphene, adding into 10ml of DMF, and performing ultrasonic treatment for 0.5 h; dropping the dispersion liquid of the ATA-grafted graphene into the xylene solution of the ATA-grafted SEBS, performing ultrasonic treatment for 1h until the graphene is uniformly dispersed in the solvent, and performing oil bath stirring on the mixed liquid at the temperature of 80 ℃ for 2.5 h. And after the reaction is finished, pouring the reaction product into 100mL of ethanol for precipitation and filtration, drying the obtained product at 100 ℃ to remove the residual solvent, carrying out hot pressing at 160 ℃ for 25min, and carrying out pressure maintaining for 2h for molding to finally obtain the graphene/SEBS composite material with the graphene addition of 0.75 wt%.

7. And (3) performing a mechanical tensile reciprocating test on the prepared graphene/SEBS composite material, wherein in the first tensile cycle, the energy dissipation value of the graphene/SEBS composite material is increased by 61% compared with that of the SEBS, and the tensile modulus of the graphene/SEBS composite material is increased by 130% compared with that of the SEBS, as shown in FIG. 1. Dynamic thermo-mechanical property tests are carried out on the prepared graphene/SEBS composite material, tan delta of the graphene/SEBS composite material is increased by 46% compared with SEBS, and elastic modulus of the graphene/SEBS composite material is increased by 121% compared with SEBS, as shown in figure 2.

Example 2

1. preparing 100mL of 1mg/mL GO/water dispersion prepared by a Hummers chemical oxidation method, wherein the atomic ratio of oxygen elements of GO is 45%, the GO sheet layer contains carboxyl, epoxy, hydroxyl and carbonyl functional groups, the diameter of the sheet layer is 1-5 mu m, the number of the sheet layers is a single layer, and 1g of EDC and 0.3g of ATA are weighed and added into the GO water dispersion for ultrasonic dispersion for 0.5 h. And placing the ultrasonic dispersion liquid into a conical flask, stirring and reacting under a constant-temperature digital display magnetic stirrer, stirring at normal temperature for 6 hours, and then stirring and reacting under an oil bath at 85 ℃ for 3 hours.

2. After the reaction is finished, 0.5g of vitamin C is additionally added into the reaction solution, the reaction is continuously stirred at 55 ℃ for 20 hours, the reaction product is filtered by an aqueous filter membrane, the washing is repeatedly carried out for three times, and the ATA grafted graphene is obtained after freeze drying, wherein the atomic percent of nitrogen element is 6.32%, the atomic percent of oxygen element is 20.75%, and the diameter of a lamella is 1-5 μm.

3. 60g of SEBS, 15g of maleic anhydride and 1g of DCP are uniformly mixed in advance and then added into an internal mixer, the mixture is mixed for 10min at 160 ℃, products are dissolved by xylene after the reaction is finished, the solution is poured into a large amount of acetone, precipitates are obtained by filtration, the products are repeatedly washed for three times, and the MAH-SEBS is obtained after vacuum drying at 60 ℃.

4. And calibrating the grafting rate of the MAH in the MAH-SEBS to be 2.14 percent by taking 0.1mol/L KOH/ethanol solution and 0.1mol/L HCl-isopropanol solution as titration standard samples.

5. 30g of MAH-SEBS and 0.50g of ATA are mixed uniformly in advance and then added into an internal mixer to be mixed for 10min at 70 ℃ to obtain the ATA grafted SEBS.

6. Weighing 5g of ATA grafted SEBS in a beaker filled with 50mL of dimethylbenzene, and placing the beaker in an oil bath at 60 ℃ until the SEBS is completely dissolved; weighing 25mg of ATA grafted graphene, adding the ATA grafted graphene into 10ml of DMF, and carrying out ultrasonic treatment for 0.5 h; dropping the dispersion liquid of the ATA-grafted graphene into the xylene solution of the ATA-grafted SEBS, performing ultrasonic treatment for 1h until the graphene is uniformly dispersed in the solvent, and performing oil bath stirring on the mixed liquid for 3h at 60 ℃. And after the reaction is finished, pouring the reaction product into 100mL of ethanol for precipitation and filtration, drying the obtained product at 100 ℃ to remove the residual solvent, carrying out hot pressing at 160 ℃ for 25min, and carrying out pressure maintaining for 2h for molding to finally obtain the graphene/SEBS composite material with the graphene addition of 0.5 wt%.

7. And (3) performing a mechanical tensile reciprocating test on the prepared graphene/SEBS composite material, wherein in the first tensile cycle, the energy dissipation value of the graphene/SEBS composite material is increased by 43% compared with that of the SEBS, and the tensile modulus is increased by 109% compared with that of the SEBS. The dynamic thermo-mechanical property test is carried out on the prepared graphene/SEBS composite material, the tan delta of the graphene/SEBS composite material is increased by 24% compared with SEBS, and the elastic modulus is increased by 85% compared with SEBS.

Example 3

1. preparing 100mL of 1mg/mL GO/water dispersion prepared by an electrolytic oxidation graphite method, wherein the atomic ratio of oxygen elements of GO is 36%, the GO lamellar contains carboxyl, epoxy, hydroxyl and carbonyl functional groups, the diameter of the lamellar is 100 nm-3 mu m, the number of lamellar layers is a single layer, weighing 1g of EDC and 0.3g of 2-aminopyridine, adding the EDC and the 2-aminopyridine into the GO water dispersion, and ultrasonically dispersing for 0.5 h. And placing the ultrasonic dispersion liquid into a conical flask, stirring and reacting under a constant-temperature digital display magnetic stirrer, stirring at normal temperature for 5 hours, and then stirring and reacting under an oil bath at 95 ℃ for 2 hours.

2. After the reaction is finished, 0.5g of vitamin C is additionally added into the reaction solution, the reaction is continuously stirred at the temperature of 55 ℃ for 24 hours, the reaction product is filtered by a water-based filter membrane, the washing is repeatedly carried out for three times, and the 2-aminopyridine grafted graphene is obtained after freeze drying, wherein the atomic percent of nitrogen elements is 4.82%, the atomic percent of oxygen elements is 15.38%, and the diameter of a lamella is 100 nm-3 mu m.

3. 60g of SEBS, 10g of maleic anhydride and 0.5g of DCP are uniformly mixed in advance and then added into an internal mixer, the mixture is mixed for 8min at the temperature of 170 ℃, products are dissolved by xylene after the reaction is finished, the solution is poured into a large amount of acetone, precipitates are obtained by filtration, the products are repeatedly washed for three times, and the MAH-SEBS is obtained after vacuum drying at the temperature of 60 ℃.

4. And calibrating the grafting rate of the MAH in the MAH-SEBS to be 1.87 percent by taking 0.1mol/L KOH/ethanol solution and 0.1mol/L HCl-isopropanol solution as titration standard samples.

5. And (3) uniformly mixing 30g of MAH-SEBS and 0.70g of 2-aminopyridine in advance, adding the mixture into an internal mixer, and mixing for 8min at 80 ℃ to obtain the 2-aminopyridine grafted SEBS.

6. Weighing 5g of the SEBS grafted by the 2-aminopyridine in a beaker filled with 80mL of dimethylbenzene, and placing the SEBS in an oil bath at 80 ℃ until the SEBS is completely dissolved; weighing 50mg of 2-aminopyridine grafted graphene, adding the graphene into 15ml of DMF, and carrying out ultrasonic treatment for 0.5 h; and (3) dripping the dispersion liquid of the 2-aminopyridine grafted graphene into the xylene solution of the 2-aminopyridine grafted SEBS, performing ultrasonic treatment for 1.5h until the graphene is uniformly dispersed in the solvent, and performing oil bath stirring on the mixed solution for 3h at 70 ℃. And after the reaction is finished, pouring the reaction product into a large amount of ethanol for precipitation and filtration, drying the obtained product at 110 ℃ to remove the residual solvent, then carrying out hot pressing at 170 ℃ for 20min, and carrying out pressure maintaining for 2h for molding to finally obtain the graphene/SEBS composite material with the graphene addition of 1 wt%.

7. And (3) performing a mechanical tensile reciprocating test on the prepared graphene/SEBS composite material, wherein in the first tensile cycle, the energy dissipation value of the graphene/SEBS composite material is increased by 68% compared with that of the SEBS, and the tensile modulus is increased by 145% compared with that of the SEBS. The dynamic thermo-mechanical property test is carried out on the prepared graphene/SEBS composite material, the tan delta of the graphene/SEBS composite material is increased by 51% compared with that of the SEBS, and the elastic modulus of the graphene/SEBS composite material is increased by 132% compared with that of the SEBS.

Example 4

1. taking GO prepared by a Hummers chemical oxidation method, preparing 100mL of 2.5mg/mL GO/water dispersion, wherein the atomic ratio of oxygen elements of GO is 40%, the GO sheet layer contains carboxyl, epoxy, hydroxyl and carbonyl functional groups, the diameter of the sheet layer is 1-5 mu m, the number of the sheet layers is a single layer, weighing 2.5g of EDC and 0.8g of 2, 6-diaminopyridine, adding into the GO water dispersion, and ultrasonically dispersing for 0.5 h. And placing the ultrasonic dispersion liquid into a conical flask, stirring and reacting under a constant-temperature digital display magnetic stirrer, stirring at normal temperature for 5 hours, and then stirring and reacting under an oil bath at 90 ℃ for 2.5 hours.

2. After the reaction is finished, adding 1.5g of vitamin C into the reaction solution, continuously stirring and reacting for 20h at 60 ℃, filtering the reaction product by using an aqueous filter membrane, repeatedly washing for three times, and freeze-drying to obtain the 2, 6-diaminopyridine grafted graphene, wherein the atomic percent of nitrogen element is 6.15%, the atomic percent of oxygen element is 18.26%, and the diameter of the lamella is 1-5 mu m.

3. 60g of SEBS and 10g of maleic anhydride are weighed and added into a three-necked flask containing 150mL of dimethylbenzene, and the mixture is placed in an oil bath at the temperature of 80 ℃ and stirred electrically until the mixture is completely dissolved. Then the temperature is raised to 125 ℃, 2g of DCP is added drop by drop, and the reflux reaction is carried out for 5 hours. After the reaction is finished, pouring the reaction liquid into excessive ethanol, precipitating a product MAH-SEBS, removing unreacted MAH and DCP, repeatedly washing the product for three times, and drying in vacuum at 60 ℃.

4. And calibrating the grafting rate of the MAH in the MAH-SEBS to be 1.65 percent by taking 0.1mol/L KOH/ethanol solution and 0.1mol/L HCl-isopropanol solution as titration standard samples.

5. And (3) uniformly mixing 30g of MAH-SEBS and 0.80g of 2, 6-diaminopyridine in advance, adding the mixture into an internal mixer, and mixing for 10min at 70 ℃ to obtain the 2, 6-diaminopyridine grafted SEBS.

6. Weighing 5g of the SEBS grafted by the 2, 6-diaminopyridine in a beaker filled with 50mL of dimethylbenzene, and placing the beaker in an oil bath at 80 ℃ until the SEBS is completely dissolved; weighing 10mg of 2, 6-diaminopyridine grafted graphene, adding the graphene into 10ml of DMF, and carrying out ultrasonic treatment for 0.5 h; dripping the dispersion liquid of the 2, 6-diaminopyridine grafted graphene into the xylene solution of the 2, 6-diaminopyridine grafted SEBS, performing ultrasonic treatment for 1h until the graphene is uniformly dispersed in the solvent, and performing oil bath stirring on the mixed solution at the temperature of 80 ℃ for 2.5 h. And after the reaction is finished, pouring the reaction product into a large amount of ethanol for precipitation and filtration, drying the obtained product at 110 ℃ to remove the residual solvent, carrying out hot pressing at 160 ℃ for 25min, and maintaining the pressure for 2h for molding to finally obtain the graphene/SEBS composite material with the graphene addition of 0.2 wt%.

7. And (3) performing a mechanical tensile reciprocating test on the prepared graphene/SEBS composite material, wherein in the first tensile cycle, the energy dissipation value of the graphene/SEBS composite material is increased by 35% compared with that of the SEBS, and the tensile modulus is increased by 95% compared with that of the SEBS. The dynamic thermo-mechanical property test is carried out on the prepared graphene/SEBS composite material, the tan delta of the graphene/SEBS composite material is increased by 18% compared with that of the SEBS, and the elastic modulus of the graphene/SEBS composite material is increased by 70% compared with that of the SEBS.

The embodiment result shows that the graphene/SEBS elastomer prepared by the method has obviously enhanced mechanical strength and damping characteristic compared with an SEBS matrix, the mechanical strength and damping performance of the SEBS are improved by constructing an interface hydrogen bond network between the graphene nanofiller and the polymer matrix, the application range of the SEBS material is expanded, and the method has important theoretical significance for development and design of novel high-performance damping materials.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the spirit of the invention, which falls within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The graphene/SEBS composite material with the characteristics of high strength and high damping is characterized by comprising 100 parts by weight of SEBS grafted by multiple hydrogen bond molecules and 0.1-2 parts by weight of graphene grafted by the multiple hydrogen bond molecules.

2. The high-strength high-damping graphene/SEBS composite material as claimed in claim 1, wherein the multiple hydrogen bonding molecules are: the multi-hydrogen-bond molecular hydrogen-bonding agent comprises 3-amino-1, 2,4 triazole, 2-aminopyridine, 2, 6-diaminopyridine or 2, 4-diamino-1, 3, 5-triazine, a hydrogen bond donor and an acceptor are contained in the multi-hydrogen-bond molecule, the donor and the acceptor of the multi-hydrogen-bond molecule can be associated to form a multi-hydrogen-bond network, and the multi-hydrogen-bond molecule contains a reactive amino functional group.

3. The graphene/SEBS composite material with high strength and high damping characteristics as claimed in claim 1, wherein a precursor of the SEBS grafted with the multiple hydrogen bonding molecules is SEBS grafted with maleic anhydride, and the grafting ratio of the maleic anhydride functional groups is 0.5-2.5%.

4. The graphene/SEBS composite material with high strength and high damping characteristics as claimed in claim 1, wherein the graphene grafted with multiple hydrogen bond molecules is prepared from graphene oxide prepared by a chemical oxidation method or an electrolytic oxidation graphite method, the atomic percentage of oxygen element is 30% -60%, the types of oxygen groups are carboxyl, epoxy, hydroxyl and carbonyl, the diameter of a lamella is 100 nm-10 μm, and the number of the lamella layers is 1-2.

5. The graphene/SEBS composite material with high strength and high damping characteristics as claimed in claim 4, wherein the multiple hydrogen bonding molecule grafted graphene is used, wherein the atomic percentage of nitrogen element is 3% -15%, the atomic percentage of oxygen element is 5% -30%, and the diameter of the sheet layer is 100 nm-10 μm.

6. A preparation method of the high-strength high-damping graphene/SEBS composite material as claimed in any one of claims 1 to 5, wherein the preparation method comprises the following steps:

7. The preparation method of the high-strength high-damping graphene/SEBS composite material according to claim 6, wherein in the step (1), the concentration of the aqueous dispersion of GO is 0.05-3 mg/ml, and the stirring reaction conditions for obtaining the GO modified by multiple hydrogen bond molecules are as follows: stirring for 3-8 h at normal temperature and stirring for 1-4 h in oil bath at 70-95 ℃; the mass ratio of GO to vitamin C is 1: 2-1: 10, and after the vitamin C is added, the stirring reaction temperature is 25-70 ℃.

8. The preparation method of the graphene/SEBS composite material with high strength and high damping characteristics according to claim 6, wherein in the step (2), the preparation of the maleic anhydride grafted SEBS through a solution method comprises the steps of dissolving the SEBS and MAH in a xylene or toluene solvent, dropping dicumyl peroxide (DCP), and carrying out reflux stirring reaction at 120-140 ℃ for 3-8 hours; the process for preparing the maleic anhydride grafted SEBS by the melt blending method comprises the steps of mixing the SEBS, the MAH and the DCP uniformly in advance, adding the mixture into an internal mixer, internally mixing the mixture for 5-20 min at the temperature of 140-170 ℃, and dissolving the obtained product by using xylene; in the solution method or the melt blending method, the concentration of SEBS is 0.2-2 g/mL, the mass of MAH is 5-20 wt% of the mass of SEBS, and the mass of DCP is 1-10 wt% of the mass of SEBS; and after the reaction is finished, pouring the reaction solution into ethanol, acetonitrile or acetone, filtering, cleaning and drying the precipitate to obtain the MAH-SEBS.

9. The preparation method of the high-strength high-damping graphene/SEBS composite material according to claim 6, wherein in the step (2), the solution method is used for preparing the SEBS grafted with the multiple hydrogen bond molecules, and the preparation method is characterized in that MAH-SEBS is dissolved in xylene, the multiple hydrogen bond molecules are dispersed in DMF, and the MAH-SEBS and the DMF are mixed and stirred at 60-90 ℃ for 0.5-5 h to obtain a product; the preparation method of the SEBS grafted by the multiple hydrogen bond molecules by the melt blending method comprises the steps of adding the MAH-SEBS and the multiple hydrogen bond molecules into an internal mixer, and internally mixing for 8-20 min at 60-90 ℃ to obtain a product; in the solution method or the melt blending method, the volume ratio of DMF to xylene is 1 (30-60), and the molar ratio of multiple hydrogen bond molecules to MAH grafted on SEBS is 1 (1-3).

10. The preparation method of the graphene/SEBS composite material with high strength and high damping characteristics according to claim 6, wherein in the step (3), the volume ratio of DMF to xylene in the organic solvent system is 1 (4-6), the hot press forming temperature is 150-170 ℃, the hot press forming time is 15-30 min, and the pressure maintaining time is 1-3 h.