CN115636900A - Preparation method of polyisoprene-acrylonitrile/barium titanate material with reversible crosslinking structure - Google Patents

Abstract

The invention relates to the technical field of functional polymer composite materials, in particular to a method for preparing a polyisoprene-acrylonitrile/barium titanate material with a reversible cross-linking structure. The method first uses the reaction of boric acid groups and diols to The alkene derivatives reacted with the corresponding organic molecules to synthesize two functional monomers containing dioxaborane groups, and then the functional monomers, isoprene and acrylonitrile monomers were initiated by a redox system, Perform emulsion polymerization to prepare isoprene-acrylonitrile Vitrimer copolymer with reversible cross-linking structure. Finally, two kinds of barium titanate containing dioxaborane groups are used to copolymerize with isoprene-acrylonitrile Vitrimer After heating and blending, compared with the prior art, the composite material involved in the present invention is innovative, improves the dielectric properties of the material, and has a certain self-repair function, and the synthesis process is simple to implement, and the reaction conditions are relatively low. Conducive to the realization of product industrialization.

Description

Preparation of a reversible cross-linked polyisoprene-acrylonitrile/barium titanate material method

technical field

The invention relates to the technical field of functional polymer composite materials, in particular to a polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure.

Background technique

Dielectric material is an insulating material with excellent dielectric capacity. In order to meet the miniaturization and flexibility requirements of the new generation of energy storage devices, people combine the advantages of ceramic inorganic materials and polymer organic materials, and use composite methods to obtain both It is a dielectric flexible composite material with high dielectric properties and good processability at the same time.

High-dielectric ceramic-polymer based dielectric flexible composite materials are filled with high-dielectric ceramic particles, using the characteristics of high dielectric constant of dielectric ceramics and good processability and organic compatibility of polymers to obtain Composite materials with higher dielectric constants. There have been a lot of research reports on the dielectric properties and flexibility of this material, mainly focusing on the research of dielectric elastic matrix, the research of filling particles, and the research of compounding and modification methods[. After a lot of research, people also found that increasing the amount of dielectric ceramic particles can effectively improve the dielectric properties of flexible composite materials, but a high filling amount will greatly reduce the flexibility and other functions of the material, and even lead to direct cracking and damage of the material. Therefore, strengthening the interaction between inorganic particles and polymers to achieve sufficient "compatibility" at the molecular level is the key to solving the above problems.

等在Science期刊报道了一种含二氧杂硼烷基团的Vitrimer材料的制备方法，将具有C-C骨架的聚合物改性成为动态交联结构的Vitrimer材料，实现了将常见C-C骨架塑料转变为具有独特功能的Vitrimer材料的技术创新。In recent years, a class of "supramolecular" materials called "Vitrimers" has emerged in polymers. Due to their multiple response modes and multiple functions such as self-healing, intelligent response, and shape memory, they are now It has become one of the international frontier hotspots. Vitrimer materials are essentially a type of dynamic cross-linked polymer with a special molecular structure, and the chemical bonds between the molecular chains are not fixed, but in dynamic equilibrium.

reported a preparation method of a Vitrimer material containing a dioxaborane group in the journal Science, which modified the polymer with a CC skeleton into a Vitrimer material with a dynamic crosslinking structure, and realized the transformation of common CC skeleton plastics into Technological innovation of Vitrimer material with unique functions.

At present, Vitrimer materials based on different reversible groups have been continuously researched, and reports on the excellent mechanical properties, rheological properties, and self-healing properties of such materials have also increased significantly. However, the research on filled Vitrimer-type composites is basically blank, which is mainly attributed to the need for a corresponding cross-linked structure between the filler and the polymer. Therefore, research in this field is groundbreaking and urgent.

In summary, although there are many polymer/barium titanate composite materials that have appeared on the market, there are still the following deficiencies:

(1) The modified barium titanate prepared by modifying the surface of filler particles with common organic substances such as coupling agents usually cannot form a chemical bond with the polymer molecular chain, resulting in insufficient adhesion between barium titanate and the matrix, affecting Comprehensive properties of composite materials.

(2) Traditional cross-linked composite materials, due to irreversible cross-linking, once the cross-linked structure is formed in the polymer and filler system, do not have reworkability. Compared with Vitrimer materials with dynamic cross-linked structure, they lack material Structural basis for functionalization.

To this end, we provide a polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure to solve this problem.

Contents of the invention

The purpose of the present invention is to solve the shortcomings in the prior art, and propose an innovative composite material, which improves the dielectric properties of the material, and has a certain self-repair function, and the synthesis process is simple to implement, and the reaction conditions are relatively low. A polyisoprene-acrylonitrile/barium titanate material with a reversible cross-linked structure, which is very beneficial to realize the advantages of the product industry, can solve this problem.

In order to achieve the above object, the present invention adopts the following technical solutions:

Design a polyisoprene-acrylonitrile/barium titanate material with reversible crosslinking structure,

A method for preparing a polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure, characterized in that it specifically comprises the following steps:

S1, first, utilize the reaction of boronic acid group and diol, alkene derivative (3-allyloxy-1,2-propanediol and 4-vinylphenylboronic acid) and corresponding organic molecule (phenylboronic acid and 1 , 2-propanediol) reaction, synthesize two kinds of functional monomers (monomer A and monomer B) containing dioxaborane group;

S2. Next, the functional monomers, isoprene and acrylonitrile monomers are initiated by a redox system to carry out emulsion polymerization to prepare an isoprene-acrylonitrile Vitrimer copolymer with a reversible crosslinking structure;

S3. Finally, two kinds of barium titanate containing dioxaborane groups and isoprene-acrylonitrile Vitrimer copolymer were selected and blended by heating to prepare polyisoprene-propylene with reversible crosslinking structure. Nitrile/barium titanate composite.

Further, when the monomer A is prepared in the S1, 3-allyloxy-1,2-propanediol, phenylboronic acid, anhydrous magnesium sulfate and tetrahydrofuran are in a mass ratio of 1:(0.5-2):(2-5 ): (7-30) mixing, and the temperature of the reaction is room temperature, and the stirring time is 3-8h.

Further, when monomer B is prepared in S1, 4-vinylphenylboronic acid, 1,2-propylene glycol, anhydrous magnesium sulfate and tetrahydrofuran are in a mass ratio of 1:(1-3):(2-5): (7-30) Mixing, and the reaction temperature is room temperature, and the stirring time is 3-8h.

Further, when preparing the isoprene-acrylonitrile Vitrimer copolymer in S2, isoprene, acrylonitrile, monomer A, monomer B, deionized water, sodium dodecylbenzenesulfonate, oil Potassium acid potassium, tert-dodecyl mercaptan, ferrous sulfate heptahydrate, sodium edetate, sodium formaldehyde sulfite by mass ratio 1: (0.5-1.5): (0.5-1.5): (0.5-1.5): ( 5-8): (0.08-0.15): (0.05-0.1): (0.03-0.05): (0.01-0.02): (0.1-0.2): (0.2-0.5) Mix well.

Further, when preparing the isoprene-acrylonitrile Vitrimer copolymer in S2, isoprene, acrylonitrile, monomer A, monomer B, deionized water, sodium dodecylbenzenesulfonate, Potassium oleate, tert-dodecyl mercaptan, ferrous sulfate heptahydrate, sodium ethylenediamine tetraacetate, and sodium formaldehyde sulfite are mixed evenly, and then 0.01-0.03 cumene peroxide is added to the polymerization kettle under the protection of nitrogen.

Further, when the isoprene-acrylonitrile Vitrimer copolymer is prepared in S2, the reaction temperature in the polymerization tank is 5° C., and the reaction time is 5-8 hours.

Further, when the polyisoprene-acrylonitrile/barium titanate composite material is prepared in the S3, two kinds of barium titanate containing dioxaborane groups are uniformly mixed in a mass ratio of 1:(0.8-1.2). Mix and add isoprene-acrylonitrile Vitrimer copolymer at 110-130°C to mix and react.

A polyisoprene-acrylonitrile/barium titanate material with a reversible cross-linking structure proposed by the present invention has the beneficial effects of:

1. The polyisoprene-acrylonitrile/barium titanate composite material with a reversible cross-linking structure involved in the present invention is innovative, and has a certain temperature response, and can form a dynamic cross-linking structure at about 70-80°C , the compatibility between the barium titanate particles and the polymer matrix is significantly improved, the interfacial cohesion is increased, the dielectric properties of the material are improved, and it has a certain self-healing function. In addition, the reversible cross-linked polyisoprene- The acrylonitrile/barium titanate composite material makes up for the blank of filled Vitrimer type composite materials at home and abroad;

2. In terms of method and technology, the present invention utilizes the reaction of specific ethylenic monomers and organic molecules to introduce dioxaborane groups into monomers for the first time. The principle is clear and the method is original. The raw materials used are 3-ene Propoxy-1,2-propanediol and phenylboronic acid are relatively cheap, the synthesis process is simple to implement, and the reaction conditions are relatively low, which is very conducive to the realization of the industrialization of the product.

Description of drawings

Fig. 1 is the schematic flow chart of the preparation of the polyisoprene-acrylonitrile/barium titanate composite material of the reversible crosslinking structure proposed by the present invention;

Fig. 2 is the infrared spectrogram of two kinds of monomers containing dioxaborane group proposed by the present invention and synthetic raw materials thereof;

Fig. 3 is the infrared spectrogram of polyisoprene-acrylonitrile/barium titanate composite material and synthetic raw material thereof that the present invention proposes;

Fig. 4 is the thermal weight loss curve of the isoprene-acrylonitrile Vitrimer copolymer proposed by the present invention and polyisoprene-acrylonitrile/barium titanate composite material;

Fig. 5 is the isoprene-acrylonitrile Vitrimer copolymer (a, × 5K times; d, × 10K times), polyisoprene-acrylonitrile/barium titanate composite material (b, × 5K times) proposed by the present invention times; e, ×10K), SEM images of two composite materials (c, surface×10 times; f, cross-section×50 times) after hot pressing for 3 hours;

Figure 6 is the dielectric constant (a) and dielectric loss (b) of the isoprene-acrylonitrile Vitrimer copolymer and polyisoprene-acrylonitrile/barium titanate composite material proposed by the present invention at different frequencies curve;

Fig. 7 is storage modulus-frequency curve (a) and loss angle-frequency curve (a) of isoprene-acrylonitrile Vitrimer copolymer and polyisoprene-acrylonitrile/barium titanate composite material proposed by the present invention-frequency curve ( b).

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention.

Example 1

3-allyloxy-1,2-propanediol (≥99%), phenylboronic acid (≥98%), 1,2-propanediol (≥99%), anhydrous magnesium sulfate (≥98%) used in this example %), tetrahydrofuran (≥99.9%), n-heptane (≥98%), 4-vinylphenylboronic acid (≥95%), isoprene (≥99%), acrylonitrile (≥99%), Sodium Dodecylbenzene Sulfonate (≥95%), Potassium Oleate (≥87%), Tertiary Dodecyl Mercaptan (≥98.5%), Ferrous Sulfate Heptahydrate (≥99.9%), Ethylenediamine Sodium tetraacetate (98%), sodium formaldehyde sulfite (≥95%) and cumene peroxide (≥97%) were all purchased from Sarn Chemical Technology (Shanghai) Co., Ltd., two kinds of dioxaborane group-containing Barium titanate is self-made according to the method in patent ZL202110646175.X.

As shown in FIG. 1 , in this example, a polyisoprene-acrylonitrile/barium titanate composite material with a reversible crosslinking structure was prepared by a three-step method. First, using the reaction of boronic acid groups with diols, alkene derivatives (3-allyloxy-1,2-propanediol and 4-vinylphenylboronic acid) were combined with corresponding organic molecules (phenylboronic acid and 1,2 -propylene glycol) reaction, synthesize two kinds of functional monomers (monomer A and monomer B) containing dioxaborane group, secondly, functional monomer, isoprene and acrylonitrile monomer, by oxidation The reduction system is initiated, and the emulsion polymerization is carried out to prepare the isoprene-acrylonitrile Vitrimer copolymer with reversible crosslinking structure. Finally, two kinds of barium titanate and isoprene-acrylonitrile containing dioxaborane groups are selected. The polyisoprene-acrylonitrile/barium titanate composite material with reversible crosslinking structure was prepared by heating and blending the acrylonitrile Vitrimer copolymer.

The specific preparation method is:

One, the preparation of two kinds of monomers containing dioxaborane group:

Monomer A: Mix 3-allyloxy-1,2-propanediol (10ml), phenylboronic acid (10g), anhydrous magnesium sulfate (30g) and tetrahydrofuran (100ml) and stir at room temperature for 6h, then filter and use Rotary evaporator concentrated under reduced pressure. The concentrated solution was poured into 100ml of n-heptane at room temperature and stirred, then allowed to stand for 30 minutes, filtered and concentrated under reduced pressure to obtain a colorless oil, which was designated as monomer-A.

Monomer B: Mix 4-vinylphenylboronic acid (10g), 1,2-propanediol (20ml), anhydrous magnesium sulfate (30g) and tetrahydrofuran (100ml) and stir at room temperature for 6h, then filter and use rotary evaporation Concentrate under reduced pressure. The suspension was poured into 100ml of n-heptane at room temperature and stirred, then allowed to stand for 30 minutes, filtered and concentrated under reduced pressure to obtain a colorless oil, which was designated as monomer-B.

Two, the preparation of the polyisoprene-acrylonitrile Vitrimer copolymer containing dioxaborane group:

Isoprene (7ml), acrylonitrile (6ml), monomer-A (6ml) and monomer-B (6ml), deionized water (40mg), sodium dodecylbenzenesulfonate (0.75g), Potassium oleate (0.5g), tertiary dodecyl mercaptan (0.25g), ferrous sulfate heptahydrate (0.1g), sodium edetate (1g), sodium formaldehyde sulfite (2.1g), under nitrogen protection Add cumene peroxide (0.125ml) into a 250ml polymerization kettle, and then react at 5°C for 7h. The isoprene-acrylonitrile Vitrimer copolymer containing dioxaborane groups is obtained after degassing, coagulation, washing and drying.

3. Preparation of polyisoprene-acrylonitrile/barium titanate composite material: According to the principle of dioxaborolane metathesis, two kinds of barium titanate containing dioxaborane groups were mixed at a ratio of 1:1. The mass ratio was uniformly mixed, and reacted at 85° C. for 2 hours to obtain reversibly cross-linked barium titanate. Then, it was added into the isoprene-acrylonitrile Vitrimer copolymer containing dioxaborane group at 120°C and mixed evenly to prepare a polyisoprene-acrylonitrile/titanium with a content of 10wt%. barium oxide composite.

The synthesized two monomers and polyisoprene-acrylonitrile/barium titanate composite were characterized by infrared. The American Nicolet Avatar 370 Fourier transform infrared spectrometer was used to test, the resolution was 2cm ^-1 , and the number of scans was 32 times. The infrared curves of the two were shown in Fig. 2 and Fig. 3 respectively, which confirmed that the single dioxaborane group body and the formation of polyisoprene-acrylonitrile/barium titanate composites.

The above-mentioned polyisoprene-acrylonitrile Vitrimer copolymer and isoprene-acrylonitrile/barium titanate composite material were characterized by thermogravimetric analysis, and tested by TGA55 thermogravimetric analyzer of American TA Company, the initial temperature was 30°C, and The heating rate of 10°C/min increased to 600°C, and the thermogravimetric curves of the two are shown in Figure 4. The results show that the addition of modified barium titanate has no effect on the thermal stability of the isoprene-acrylonitrile Vitrimer copolymer. big.

The surface morphology of the above-mentioned polyisoprene-acrylonitrile Vitrimer copolymer and isoprene-acrylonitrile/barium titanate composite was analyzed by scanning electron microscopy. After the sample is dried, it is sprayed with gold, the gold spraying current is 5-6mA, and the gold spraying time is 30s. After using the Zeiss SIGMA300 field emission scanning electron microscope to observe the scanning electron microscope picture of the barium titanate surface, as shown in Figure 5, the result is polyisoprene The alkene-acrylonitrile/barium titanate composite has a dynamic cross-linking structure, and the composite has a certain self-healing function at a certain temperature.

The dielectric properties of the above-mentioned polyisoprene-acrylonitrile Vitrimer copolymer and isoprene-acrylonitrile/barium titanate composite materials were tested, and the samples were analyzed by Agilent 4294A impedance analyzer at room temperature For the test, the test frequency is 2×10 ² -10 ⁷ Hz, and the frequency-dielectric constant and frequency-dielectric loss curves of the material are shown in Figure 6.

The above-mentioned polyisoprene-acrylonitrile Vitrimer copolymer and isoprene-acrylonitrile/barium titanate composite are subjected to dynamic mechanical analysis (DMA) analysis, and the TA Q800 DMA instrument produced by American TA Company is used for testing. Tensile mode was used, and the temperature scanning test conditions were: temperature range -110-150°C, frequency 5Hz, heating rate 5°C/min, storage modulus-frequency curve and loss angle-frequency curve are shown in Figure 7.

Through infrared spectrogram analysis, the characteristic absorption peaks of the two synthesized monomers and the polyisoprene-acrylonitrile/barium titanate composite material were compared, as shown in Figure 2 and Figure 3, as can be seen from Figure 2, the monomer A shows the absorption peak at 1306cm- ¹ with the stretching vibration of BO in dioxaborane, which is similar to phenylboronic acid, and also shows the characteristic absorption peak of CH in methylene at 2856cm ^-1 , which is similar to 3-allyl Oxy-1,2-propanediol, demonstrating the formation of monomer A containing a dioxaborane group, monomer B prepared from 4-vinylphenylboronic acid and 1,2-propanediol, monomers B and 4 -Infrared spectrum of vinylphenylboronic acid has an absorption peak at 1306cm ^-1 corresponding to BO stretching vibration in dioxaborane, and monomer B also shows two peaks at 2964cm ^-1 and 2873cm ^-1 A characteristic absorption peak, which was attributed to the CH stretching vibration in the methyl group, confirmed the formation of monomer B containing the dioxaborane group.

Two modified barium titanates (BT-A and BT-B), isoprene-acrylonitrile Vitrimer copolymer (Ploy (IP-co-AN)) and polyisoprene-acrylonitrile/barium titanate The infrared spectrum of the composite material (Ploy(IP-co-AN)/BT) is shown in Figure 3, both Ploy(IP-co-AN) and Ploy(IP-co-AN)/BT appeared at 1631cm ^-1 The characteristic absorption peak of the C=C bond, in addition, it can be seen that all the samples in Figure 3 have the stretching vibration absorption peak of BO in the dioxaborane group at 1306 cm ^-1 , which proves that the modified titanic acid Presence of dioxaborane groups in barium, isoprene-acrylonitrile Vitrimer copolymers, and polyisoprene-acrylonitrile/barium titanate composites.

Through thermogravimetric analysis, a comparative study of isoprene-acrylonitrile Vitrimer copolymer (Ploy (IP-co-AN)) and polyisoprene-acrylonitrile/barium titanate composite (Ploy (IP-co-AN) AN)/BT) thermal weight loss curve, as shown in Figure 4, as can be seen from the figure, isoprene-acrylonitrile Vitrimer copolymer and polyisoprene-acrylonitrile/barium titanate composite material behave below 200 ℃ A similar thermogravimetric curve was obtained, and the initial decomposition temperature was around 123°C, indicating that the addition of modified barium titanate had little effect on the thermal stability of the isoprene-acrylonitrile Vitrimer copolymer.

In order to study the morphology of the cross-linked structure of polyisoprene-acrylonitrile/barium titanate composite material, the present invention observes the surface topography characteristic of different barium titanate by electron scanning microscope, as shown in Figure 5, by Figure 5a It can be seen from Figure 5a and 5d that the surface of the polyisoprene-acrylonitrile/barium titanate composite material is smooth and smooth. The particles are uniformly distributed and there is no agglomeration phenomenon, indicating that the modified barium titanate has good compatibility with the matrix and has good dispersion.

In order to further study the dynamic cross-linking structure of the polyisoprene-acrylonitrile/barium titanate composite material, two composite materials were hot-pressed at 80°C for 3 hours, and then observed by SEM, as shown in Figure 5c and 5f, which can be seen , after 3 hours of hot pressing, the edges of the two pieces of material are still visible from the surface observation, but from the cross-sectional surface of the two pieces of material, it can be seen that the contact surface of the middle part of the two pieces of material has been bonded together, and the interface is blurred, indicating that the polyheterogeneous The pentadiene-acrylonitrile/barium titanate composite material has a dynamic cross-linking structure, and the composite material has a certain self-healing function at a certain temperature.

In order to study the change of the dielectric properties of the material, the isoprene-acrylonitrile Vitrimer copolymer (Ploy(IP-co-AN)) and the polyisoprene-acrylonitrile/barium titanate composite material (Ploy(IP-co-AN)) were compared. The dielectric constant and dielectric loss curves of IP-co-AN)/BT) at different frequencies are shown in Figure 6, as shown in Figure 5a, the polyisoprene-acrylonitrile/barium titanate composite The dielectric constant is higher than that of isoprene-acrylonitrile Vitrimer copolymer in the range of 2×10 ² -10 ⁷ Hz, which is attributed to the high dielectric constant of barium titanate itself, and the addition of barium titanate makes the material The interfacial polarization is enhanced, as shown in Figure 5b, the dielectric loss of the isoprene-acrylonitrile Vitrimer copolymer decreases with frequency in the lower frequency range, and increases with frequency above 6×10 ⁶ Hz, The dielectric loss of the polyisoprene-acrylonitrile/barium titanate composite decreases gradually with frequency, which can be attributed to conductance or relaxation.

In order to further study the effect of dynamic crosslinking on the dynamic mechanical properties of materials, the isoprene-acrylonitrile Vitrimer copolymer (Ploy(IP-co-AN)) and polyisoprene-acrylonitrile/barium titanate composite were compared. The dynamic mechanical analysis (DMA) curve of the material (Ploy(IP-co-AN)/BT), as shown in Figure 7, can be seen from Figure 7a, the energy storage capacity of the polyisoprene-acrylonitrile/barium titanate composite The modulus M' is higher than that of the isoprene-acrylonitrile Vitrimer copolymer without modified barium titanate, which is due to the bond between the modified barium titanate and the copolymer, resulting in reinforcement, as shown in Figure 7b , the loss peak of the polyisoprene-acrylonitrile/barium titanate composite material is smaller and wider, indicating that the addition of modified barium titanate increases the degree of crosslinking of the material to a certain extent.

To sum up, with the help of the above-mentioned technical solution of the present invention, the polyisoprene-acrylonitrile/barium titanate composite material with a reversible cross-linking structure involved in the present invention is innovative and has a certain temperature response. A dynamic cross-linking structure can be formed at about 70-80°C, the compatibility between barium titanate particles and polymer matrix is significantly improved, the interface bonding force is increased, the dielectric properties of the material are improved, and it has a certain self-healing function. In addition, The polyisoprene-acrylonitrile/barium titanate composite material with reversible crosslinking structure makes up for the blank of filled Vitrimer type composite materials at home and abroad, and the present invention utilizes specific ethylenic monomers and organic molecules to react in a single The method of introducing dioxaborane groups into the body has a clear principle and originality. The raw materials used such as 3-allyloxy-1,2-propanediol and phenylboronic acid are relatively cheap, and the synthesis process is simple to implement. Reaction conditions are relatively low, which is very conducive to realizing the industrialization of products.

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.

Claims (7)

1. A preparation method of a polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure is characterized by comprising the following steps:

s1, firstly, utilizing the reaction of boric acid group and diol to respectively react alkene derivatives (3-allyloxy-1, 2-propylene glycol and 4-vinyl phenyl boric acid) with corresponding organic molecules (phenylboronic acid and 1, 2-propylene glycol) to synthesize two functional monomers (monomer A and monomer B) containing dioxaborane group;

s2, initiating the functional monomer, isoprene and acrylonitrile monomer through a redox system, and carrying out emulsion polymerization to prepare an isoprene-acrylonitrile Vitrimer copolymer with a reversible crosslinking structure;

and S3, finally, heating and blending two barium titanate containing dioxaboronyl groups and the isoprene-acrylonitrile Vitrimer copolymer to prepare the polyisoprene-acrylonitrile/barium titanate composite material with the reversible crosslinking structure.

2. The polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure as claimed in claim 1, wherein in the preparation of the monomer A in S1, 3-allyloxy-1, 2-propanediol, phenylboronic acid, anhydrous magnesium sulfate and tetrahydrofuran are mixed according to the mass ratio of 1 (0.5-2) to (2-5) to (7-30), the reaction temperature is room temperature, and the stirring time is 3-8h.

3. The polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure as claimed in claim 1, wherein in the preparation of the monomer B in the S1, 4-vinylphenylboronic acid, 1, 2-propanediol, anhydrous magnesium sulfate and tetrahydrofuran are mixed according to the mass ratio of 1 (1-3) to (2-5) to (7-30), the reaction temperature is room temperature, and the stirring time is 3-8h.

4. The polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure as claimed in claim 1, wherein when the isoprene-acrylonitrile Vitrimer copolymer is prepared in S2, isoprene, acrylonitrile, the monomer a, the monomer B, deionized water, sodium dodecyl benzene sulfonate, potassium oleate, tert-dodecyl mercaptan, ferrous sulfate heptahydrate, sodium ethylene diamine tetracetate, sodium formaldehyde sulfite are mixed according to a mass ratio of 1: (0.5-1.5): (0.5-1.5): (0.5-1.5): (5-8): (0.08-0.15): (0.05-0.1): (0.03-0.05): (0.01-0.02): (0.1-0.2): (0.2-0.5) mixing uniformly.

5. The polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure as claimed in claim 4, wherein when preparing the isoprene-acrylonitrile Vitrimer copolymer in S2, the isoprene, the acrylonitrile, the monomer A, the monomer B, the deionized water, the sodium dodecyl benzene sulfonate, the potassium oleate, the tert-dodecyl mercaptan, the ferrous sulfate heptahydrate, the sodium ethylene diamine tetracetate and the sodium formaldehyde sulfite are mixed uniformly, and then 0.01-0.03 of dicumyl peroxide is added into a polymerization kettle under the protection of nitrogen.

6. The polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure as claimed in claim 5, wherein the temperature for the reaction in the polymerization kettle is 5 ℃ and the reaction time is 5-8h when the isoprene-acrylonitrile Vitrimer copolymer is prepared in S2.

7. The polyisoprene-acrylonitrile/barium titanate material with a reversible crosslinking structure as claimed in claim 1, wherein in the preparation of the polyisoprene-acrylonitrile/barium titanate composite material in S3, two barium titanates with dioxaboronyl groups are uniformly mixed according to the mass ratio of 1 (0.8-1.2), and are added into the isoprene-acrylonitrile Vitrimer copolymer at 110-130 ℃ for mixing reaction.

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