A graphene / ammonium molybdate synergistically modified PVC composite material and its preparation method and application

Abstract

The present invention belongs to the technical field of composite material preparation, and specifically relates to a graphene / ammonium molybdate synergistically modified PVC composite material, and its preparation method and application. The present invention uses a ball milling method to ball mill graphite powder, ammonium molybdate and PVC resin together, and can coat the graphene on the surface of the PVC resin while mechanically exfoliating the graphene, so that the graphene is uniformly dispersed in the PVC resin, and the ammonium molybdate is uniformly dispersed in the PVC resin. The present invention adds a small amount of graphene / ammonium molybdate to significantly improve the thermal stability of the PVC resin. The preparation method provided by the present invention combines graphene and ammonium molybdate to synergistically form a graphene / ammonium molybdate synergistically modified PVC composite material, which gives full play to the role of two-dimensional materials in thermal and physical barriers, and at the same time, the addition of ammonium molybdate inhibits the thermal decomposition of the PVC resin.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite material preparation, and in particular relates to a graphene / ammonium molybdate synergistically modified PVC composite material, a preparation method and an application thereof. Background Art

[0002] Polyvinyl chloride (PVC) resin is a thermoplastic material widely used in industries such as packaging, military, and construction due to its high strength, corrosion resistance, low cost, and easy processing. However, PVC resin has poor thermal stability. When processed at temperatures above 120°C, structural defects within its molecules can cause degradation, resulting in poor performance and severely inhibiting its application.

[0003] In order to improve the thermal stability of PVC resin, researchers currently use a method that is commonly used to add stabilizers during the processing of PVC resin, such as metal soaps, lead salts and organotin compound heat stabilizers, but this method is costly and toxic to the human body.

[0004] Chinese patent CN114957882A discloses a PVC composition containing a high molecular weight heat stabilizer, as well as its preparation method and application. The disclosed PVC composition comprises PVC resin, a high molecular weight heat stabilizer containing NH2, NMe2, or NEt2 as a functional group, an inorganic filler, a processing aid, an impact modifier, a light stabilizer, a lubricant, and a titanium dioxide component. The resulting PVC resin material exhibits a certain degree of thermal stability, but the thermal stability is still not ideal. Summary of the Invention

[0005] The purpose of the present invention is to provide a graphene / ammonium molybdate synergistically modified PVC composite material and a preparation method and application thereof. The graphene / ammonium molybdate synergistically modified PVC composite material provided by the present invention has good thermal stability.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a graphene / ammonium molybdate synergistically modified PVC composite material, which is made from the following raw materials in parts by weight:

[0008] 70-120 parts of PVC resin, 0.1-3 parts of graphite powder, 30-60 parts of plasticizer and 0.001-0.5 parts of ammonium molybdate.

[0009] Preferably, the plasticizer includes one or more of dibutyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate and di(2-ethyl)hexyl phthalate.

[0010] Preferably, the particle size of the graphite powder is 325-8000 mesh.

[0011] The present invention also provides a method for preparing the graphene / ammonium molybdate synergistically modified PVC composite material described in the above scheme, comprising the following steps:

[0012] (1) mixing PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution, and then ball milling and drying in sequence to obtain graphene / ammonium molybdate-PVC mixed powder;

[0013] The ball milling beads used in the ball mill include small ball milling balls, medium ball milling balls and large ball milling balls; the particle size of the small ball milling balls is 1 to 4 mm, the particle size of the medium ball milling balls is 4.1 to 9.0 mm, and the particle size of the large ball milling balls is 9.1 to 15.0 mm; the mass ratio of the small ball milling balls to the medium ball milling balls is 1 to 10:5 to 20; the mass ratio of the medium ball milling balls to the large ball milling balls is 5 to 20:15 to 40;

[0014] (2) The graphene / ammonium molybdate-PVC mixed powder and the plasticizer are mixed and then plasticized and hot-pressed to obtain a graphene / ammonium molybdate synergistically modified PVC composite material.

[0015] Preferably, the ammonium molybdate ethanol aqueous solution comprises ammonium molybdate, anhydrous ethanol and water; the mass ratio of the ammonium molybdate to water is 0.01-0.5:10-50, and the mass ratio of the total mass of the ammonium molybdate and water to the anhydrous ethanol is 10-50:40-90.

[0016] Preferably, the ball milling speed is 400-1600 r / min, and the ball milling time is 12-48 h; the mass ratio of the total mass of the PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution to the ball milling beads is 96-128:40-80.

[0017] Preferably, the drying temperature is 40 to 80° C., and the insulation time is 10 to 24 hours.

[0018] Preferably, the plasticizing temperature is 120-160° C., and the holding time is 6-14 minutes.

[0019] Preferably, the temperature of the hot pressing molding is 120-160° C., the pressure is 1-4 MPa, and the holding time is 2-10 min.

[0020] The present invention also provides the use of the graphene / ammonium molybdate synergistically modified PVC composite material described in the above scheme or the graphene / ammonium molybdate synergistically modified PVC composite material obtained by the preparation method described in the above scheme in thermal and physical barriers.

[0021] The present invention provides a graphene / ammonium molybdate synergistically modified PVC composite material, which is made from the following raw materials in parts by weight: 70-120 parts of PVC resin, 0.1-3 parts of graphite powder, 30-60 parts of plasticizer, and 0.001-0.5 parts of ammonium molybdate. In the graphene / ammonium molybdate synergistically modified PVC composite material provided by the present invention, graphene and ammonium molybdate are evenly distributed in the PVC resin. The synergistic effect of the graphene and ammonium molybdate makes the graphene / ammonium molybdate synergistically modified PVC composite material have excellent thermal stability, and its T 10 Above 253℃, T 50 Above 307℃.

[0022] The present invention also provides a method for preparing the graphene / ammonium molybdate synergistically modified PVC composite material described in the above scheme. The present invention uses a ball milling method to ball-mill graphite powder, ammonium molybdate and PVC resin together, and can coat the graphene on the surface of the PVC resin while mechanically exfoliating the graphene, so that the graphene is uniformly dispersed in the PVC resin, and the ammonium molybdate is uniformly dispersed in the PVC resin. The present invention adds a small amount of graphene / ammonium molybdate to significantly improve the thermal stability of the PVC resin. The preparation method provided by the present invention combines graphene and ammonium molybdate to synergistically form a graphene / ammonium molybdate synergistically modified composite material, giving full play to the role of two-dimensional materials in thermal and physical barriers, and at the same time, the addition of ammonium molybdate inhibits the thermal decomposition of the PVC resin. The preparation method provided by the present invention has simple steps, is green and pollution-free, and has prospects for industrial production.

[0023] The present invention also provides the use of the graphene / ammonium molybdate synergistically modified PVC composite material described in the above embodiment, or the graphene / ammonium molybdate synergistically modified PVC composite material obtained by the preparation method described in the above embodiment, in thermal and physical barrier applications. The present invention utilizes the graphene / ammonium molybdate synergistically modified PVC composite material for thermal and physical barrier applications, exhibiting advantages such as good thermal stability, long service life, and low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0025] Figure 1 This is a SEM image of graphene obtained after etching the graphene / PVC mixed powder prepared in Comparative Example 1 of the present invention;

[0026] Figure 2These are TGA graphs of the graphene / PVC composite material prepared in Comparative Example 1 of the present invention, the graphene / ammonium molybdate synergistically reinforced PVC composite material prepared in Examples 1 and 2, and unmodified PVC. DETAILED DESCRIPTION

[0027] The present invention provides a graphene / ammonium molybdate synergistically modified PVC composite material, which is made from the following raw materials in parts by weight:

[0028] 70-120 parts of PVC resin, 0.1-3 parts of graphite powder, 30-60 parts of plasticizer and 0.001-0.5 parts of ammonium molybdate.

[0029] The graphene / ammonium molybdate synergistically modified PVC composite material provided by the present invention comprises 70 to 120 parts of PVC resin, preferably 80 to 110 parts, and more preferably 90 to 100 parts.

[0030] The graphene / ammonium molybdate synergistically modified PVC composite material provided by the present invention comprises 0.1 to 3 parts of graphite powder, preferably 0.5 to 2.5 parts, and more preferably 1.0 to 2.0 parts; the particle size of the graphite powder is preferably 325 to 8000 mesh, more preferably 500 to 5000 mesh, and further preferably 1000 to 2000 mesh.

[0031] The graphene / ammonium molybdate synergistically modified PVC composite material provided by the present invention comprises 30 to 60 parts of a plasticizer, preferably 35 to 55 parts, and more preferably 40 to 50 parts; the plasticizer preferably comprises one or more of dibutyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate, and di(2-ethyl)hexyl phthalate.

[0032] The graphene / ammonium molybdate synergistically modified PVC composite material provided by the present invention comprises 0.001 to 0.5 parts of ammonium molybdate, preferably 0.01 to 0.3 parts, and more preferably 0.05 to 0.1 parts.

[0033] The present invention also provides a method for preparing the graphene / ammonium molybdate synergistically modified PVC composite material described in the above scheme, comprising the following steps:

[0034] (1) mixing PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution, and then ball milling and drying in sequence to obtain graphene / ammonium molybdate-PVC mixed powder;

[0035] The ball milling beads used in the ball mill include small ball milling balls, medium ball milling balls and large ball milling balls; the particle size of the small ball milling balls is 1 to 4 mm, the particle size of the medium ball milling balls is 4.1 to 9.0 mm, and the particle size of the large ball milling balls is 9.1 to 15.0 mm; the mass ratio of the small ball milling balls to the medium ball milling balls is 1 to 10:5 to 20; the mass ratio of the medium ball milling balls to the large ball milling balls is 5 to 20:15 to 40;

[0036] (2) The graphene / ammonium molybdate-PVC mixed powder and the plasticizer are mixed and then plasticized and hot-pressed to obtain a graphene / ammonium molybdate synergistically modified PVC composite material.

[0037] The present invention comprises mixing PVC resin, graphite powder, and an aqueous ammonium molybdate ethanol solution, followed by ball milling and drying to obtain a graphene / ammonium molybdate-PVC mixed powder. In the present invention, the aqueous ammonium molybdate ethanol solution preferably comprises ammonium molybdate, anhydrous ethanol, and water. The method for preparing the ammonium molybdate solution preferably comprises the following steps: premixing ammonium molybdate and water, and then mixing the resulting premix with anhydrous ethanol to obtain the ammonium molybdate solution.

[0038] In the present invention, the ammonium molybdate preferably includes ammonium molybdate containing crystalline water and ammonium molybdate not containing crystalline water; the amount of crystalline water in the ammonium molybdate containing crystalline water is preferably 4 or 6; the mass ratio of the ammonium molybdate to water is preferably 0.01-0.5:10-50, more preferably 0.05-0.3:25-45, and further preferably 0.1-0.2:30-40; the mass ratio of the total mass of the ammonium molybdate and water to anhydrous ethanol is preferably 10-50:40-90, more preferably 15-45:50-80, and further preferably 20-40:60-70; and the water is preferably ultrapure water.

[0039] In the present invention, the ball milling preferably includes the following steps: placing the mixture obtained by mixing PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution and ball milling beads in a ball milling jar, stirring evenly with a glass rod, and then placing the ball milling jar in a ball mill for ball milling.

[0040] In the present invention, the ball milling speed is preferably 400-1600 r / min, more preferably 600-1400 r / min, and further preferably 800-1200 r / min; the ball milling time is preferably 12-48 h, more preferably 16-42 h, and further preferably 22-36 h; the mass ratio of the total mass of the PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution to the ball milling beads is preferably 96-128:40-80, more preferably 100-125:50-70, and further preferably 110-120:55-65.

[0041] In the present invention, the ball milling beads used in the ball mill preferably include small ball milling balls, medium ball milling balls and large ball milling balls; the particle size of the small ball milling balls is preferably 1-4 mm, more preferably 1.5-3.5 mm, and further preferably 2.0-3.0 mm; the particle size of the medium ball milling balls is preferably 4.1-9.0 mm, more preferably 4.5-8.0 mm, and further preferably 5.0-7.0 mm; the particle size of the large ball milling balls is preferably 9.1-15.0 mm, more preferably 9.5-14 mm, and further preferably 10.0-13.0 mm.

[0042] In the present invention, the mass ratio of the small ball milling balls to the medium ball milling balls is preferably 1-10:5-20, more preferably 3-8:8-15, and further preferably 5-7:10-13; the mass ratio of the medium ball milling balls to the large ball milling balls is preferably 5-20:15-40, more preferably 9-18:20-35, and further preferably 11-15:25-30.

[0043] In the present invention, the drying temperature is preferably 40-80°C, more preferably 50-70°C, the holding time is preferably 10-24 hours, more preferably 15-20 hours; and the drying equipment is preferably an oven. The present invention removes ultrapure water and anhydrous ethanol from the ball-milled product by drying.

[0044] In the present invention, the obtained product is preferably sieved after drying; the aperture of the sieve is preferably based on the target particle size of the graphene / ammonium molybdate-PVC mixed powder; the target particle size of the graphene / ammonium molybdate-PVC mixed powder is preferably 325 to 8000 mesh, more preferably 500 to 5000 mesh, and further preferably 1000 to 2000 mesh.

[0045] After obtaining the graphene / ammonium molybdate-PVC mixed powder, the present invention mixes the graphene / ammonium molybdate-PVC mixed powder with a plasticizer, then sequentially plasticizes and hot-presses to obtain a graphene / ammonium molybdate synergistically modified PVC composite material. In the present invention, the plasticizing temperature is preferably 120-160°C, more preferably 130-150°C, and the holding time is preferably 6-14 minutes, more preferably 8-12 minutes. The plasticizing is preferably performed in a mold and an oven.

[0046] In the present invention, the temperature of the hot pressing molding is preferably 120-160°C, more preferably 130-150°C, the pressure is preferably 1-4 MPa, more preferably 2-3 MPa, and the holding time is preferably 2-10 min, more preferably 4-8 min; the equipment for the hot pressing molding is preferably a hot press.

[0047] The present invention also provides the use of the graphene / ammonium molybdate synergistically modified PVC composite material described in the above scheme or the graphene / ammonium molybdate synergistically modified PVC composite material obtained by the preparation method described in the above scheme in thermal and physical barriers.

[0048] In order to further illustrate the present invention, the scheme of the present invention is described in detail below with reference to the accompanying drawings and embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0049] Example 1

[0050] (1) preparing an ammonium molybdate solution: dissolving 0.01 g of ammonium molybdate in 30 g of ultrapure water to obtain a premixed solution, and then adding 70 g of anhydrous ethanol to the premixed solution to obtain an ammonium molybdate solution;

[0051] (2) 10 g of PVC resin, 2 g of graphite powder, 10 g of the ammonium molybdate ethanol solution, and 60 g of ball milling beads were placed in a ball mill and stirred with a glass rod;

[0052] (3) placing the ball milling jar into a ball mill for ball milling at a ball milling speed of 800 r / min and a ball milling time of 36 h, wherein the mass ratio of the total mass of the PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution to the ball milling beads is 96:80, and the ball milling beads used for ball milling include small ball milling balls, medium ball milling balls and large ball milling balls, the particle size of the small ball milling balls is 3.5 mm, the particle size of the medium ball milling balls is 8.0 mm, and the particle size of the large ball milling balls is 14 mm, the mass ratio of the small ball milling balls to the medium ball milling balls is 10:5, and the mass ratio of the medium ball milling balls to the large ball milling balls is 20:25; after ball milling, placing the ball milling jar containing the materials into an oven for drying at a drying temperature of 60° C. and a drying time of 12 h to remove ultrapure water and anhydrous ethanol; and then sieving with a mesh sieve to obtain a graphene / ammonium molybdate-PVC mixed powder;

[0053] (4) The graphene / ammonium molybdate synergistically modified PVC mixed powder and the plasticizer are uniformly mixed in a mass ratio of 10:4, and the mixed material is then placed in a mold. Finally, the mold containing the material is placed in an oven for plasticization at a plasticizing temperature of 140°C and a plasticizing time of 10 minutes to obtain a plasticized material; finally, the plasticized material is hot-pressed at a hot-pressing temperature of 150°C and a hot-pressing time of 3 minutes to obtain a graphene / ammonium molybdate synergistically modified PVC composite material.

[0054] Example 2

[0055] (1) preparing an ammonium molybdate solution: dissolving 0.1 g of ammonium molybdate in 30 g of ultrapure water to obtain a premixed solution, and then adding 70 g of anhydrous ethanol to the premixed solution to obtain an ammonium molybdate solution;

[0056] (2) 10 g of PVC resin, 2 g of graphite powder, 10 g of the ammonium molybdate ethanol solution, and 60 g of ball milling beads were placed in a ball mill and stirred with a glass rod;

[0057] (3) placing the ball milling jar into a ball mill for ball milling at a ball milling speed of 800 r / min and a ball milling time of 36 h, wherein the mass ratio of the total mass of the PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution to the ball milling beads is 96:80, and the ball milling beads used for ball milling include small ball milling balls, medium ball milling balls and large ball milling balls, the particle size of the small ball milling balls is 3.5 mm, the particle size of the medium ball milling balls is 8.0 mm, and the particle size of the large ball milling balls is 14 mm, the mass ratio of the small ball milling balls to the medium ball milling balls is 10:5, and the mass ratio of the medium ball milling balls to the large ball milling balls is 20:25; after ball milling, placing the ball milling jar containing the materials into an oven for drying at a drying temperature of 60° C. and a drying time of 12 h to remove ultrapure water and anhydrous ethanol; and then sieving with a mesh sieve to obtain a graphene / ammonium molybdate-PVC mixed powder;

[0058] (4) The graphene / ammonium molybdate-PVC mixed powder and the plasticizer are uniformly mixed in a mass ratio of 10:4, and the mixed material is then placed in a mold. Finally, the mold containing the material is placed in an oven for plasticization at a plasticizing temperature of 140° C. and a plasticizing time of 10 min to obtain a plasticized material; finally, the plasticized material is hot-pressed at a hot-pressing temperature of 150° C. and a hot-pressing time of 3 min to obtain a graphene / ammonium molybdate-PVC composite material.

[0059] Comparative Example 1

[0060] (1) Place 10 g of PVC resin, 2 g of graphite powder, and 60 g of ball milling beads in a ball mill and stir with a glass rod to mix.

[0061] (2) placing the ball milling jar into a ball mill for ball milling at a ball milling speed of 800 r / min and a ball milling time of 36 h, wherein the mass ratio of the total mass of the PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution to the ball milling beads is 96:80, and the ball milling beads used for ball milling include small ball milling balls, medium ball milling balls and large ball milling balls, the particle size of the small ball milling balls is 3.5 mm, the particle size of the medium ball milling balls is 8.0 mm, and the particle size of the large ball milling balls is 14 mm, the mass ratio of the small ball milling balls to the medium ball milling balls is 10:5, and the mass ratio of the medium ball milling balls to the large ball milling balls is 20:25; after ball milling, placing the ball milling jar containing the materials into an oven for drying at a drying temperature of 60° C. and a drying time of 12 h to remove ultrapure water and anhydrous ethanol; and then sieving with a mesh sieve to obtain a graphene / PVC mixed powder;

[0062] (3) The graphene / PVC mixed powder and the plasticizer are uniformly mixed in a mass ratio of 10:4, and the mixed material is then placed in a mold. Finally, the mold containing the material is placed in an oven for plasticization at a plasticizing temperature of 140° C. and a plasticizing time of 10 min to obtain a plasticized material; finally, the plasticized material is hot-pressed at a hot-pressing temperature of 150° C. and a hot-pressing time of 3 min to obtain a graphene / PVC composite material.

[0063] The graphene / PVC mixed powder prepared in this comparative example was added to a beaker filled with cyclohexanone and stirred thoroughly until the PVC was dissolved in the cyclohexanone to obtain a graphene dispersion. A copper mesh was used to scoop out graphene from the obtained graphene dispersion, and the copper mesh was then placed under an infrared lamp for drying to obtain a graphene sample. The graphene sample was observed using a scanning electron microscope. The results are as follows: Figure 1 As shown. Figure 1 It can be seen that graphene can be prepared by grinding graphite using the in-situ ball milling method of the present invention.

[0064] Thermogravimetric tests were performed on unmodified PVC, the graphene / ammonium molybdate-PVC composite materials prepared in Examples 1 and 2, and the graphene / PVC composite materials prepared in Comparative Example 1 using a TGA-2 (SF) thermogravimetric instrument. The test temperature range was 30-800°C, the heating rate was 10°C / min, and the test atmosphere was nitrogen. The results are shown in Tables 1 and Figure 2 shown.

[0065] Table 1 Thermogravimetric test results of unmodified PVC, graphene / ammonium molybdate-PVC composite materials prepared in Examples 1 to 2, and graphene / PVC composite materials prepared in Comparative Example 1

[0066]

[0067] According to Table 1 and Figure 2 It can be seen that compared with unmodified PVC, the T 10 、T 50 and T max1 The temperature of graphene / ammonium molybdate-PVC composite material increased by 3℃, 17℃ and 14℃ respectively, and the residual carbon content increased by 2.6%. 10 、T 50 and T max1 The temperature of graphene / PVC composite material increased by 4℃, 21℃ and 16℃ respectively, and the residual carbon content increased by 4.5%. 10 、T 50 and T max1The temperature increased by 2°C, 6°C and 5°C respectively, and the residual carbon content increased by 1.7%; the above results show that the thermal stability of the PVC composite material with the simultaneous addition of graphene and ammonium molybdate is significantly better than that of the PVC composite material with only graphene added. This shows that graphene and ammonium molybdate have a synergistic effect, which can further improve the thermal stability of PVC.

[0068] From the above examples, it can be seen that the thermal stability of the graphene / ammonium molybdate synergistically modified PVC composite material prepared by the present invention is significantly improved. 10 Above 253℃, T 50 Above 307℃.

[0069] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A graphene / ammonium molybdate synergistically modified PVC composite material, made from a graphene / ammonium molybdate-PVC mixed powder and a plasticizer, wherein the graphene / ammonium molybdate-PVC mixed powder is prepared from the following raw materials in parts by weight: 70-120 parts of PVC resin, 0.1-3 parts of graphite powder and 0.001-0.5 parts of ammonium molybdate; The mass fraction of the plasticizer is 30 to 60 parts; The preparation method of the graphene / ammonium molybdate-PVC mixed powder comprises the following steps: PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution are mixed and then ball-milled and dried in sequence to obtain graphene / ammonium molybdate-PVC mixed powder; the ball milling beads used in the ball milling include small ball milling balls, medium ball milling balls and large ball milling balls; the particle size of the small ball milling balls is 1-4 mm, the particle size of the medium ball milling balls is 4.1-9.0 mm, and the particle size of the large ball milling balls is 9.1-15.0 mm; the mass ratio of the small ball milling balls to the medium ball milling balls is 1-10:5-20; and the mass ratio of the medium ball milling balls to the large ball milling balls is 5-20:15-40.

2. The graphene / ammonium molybdate synergistically modified PVC composite material according to claim 1, characterized in that: The plasticizer includes one or more of di-n-octyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate and di(2-ethyl)hexyl phthalate.

3. The graphene / ammonium molybdate synergistically modified PVC composite material according to claim 1, characterized in that: The particle size of the graphite powder is 325-8000 mesh.

4. The method for preparing the graphene / ammonium molybdate synergistically modified PVC composite material according to any one of claims 1 to 3, characterized in that: The following steps are involved: (1) PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution are mixed, ball milled and dried in sequence to obtain graphene / ammonium molybdate-PVC mixed powder; The ball milling beads used in the ball mill include small ball milling balls, medium ball milling balls and large ball milling balls; the particle size of the small ball milling balls is 1-4 mm, the particle size of the medium ball milling balls is 4.1-9.0 mm, and the particle size of the large ball milling balls is 9.1-15.0 mm; the mass ratio of the small ball milling balls to the medium ball milling balls is 1-10:5-20; the mass ratio of the medium ball milling balls to the large ball milling balls is 5-20:15-40; (2) The graphene / ammonium molybdate-PVC mixed powder and the plasticizer are mixed and then plasticized and hot-pressed to obtain a graphene / ammonium molybdate synergistically modified PVC composite material.

5. The preparation method according to claim 4, characterized in that The ammonium molybdate ethanol aqueous solution comprises ammonium molybdate, anhydrous ethanol and water; the mass ratio of the ammonium molybdate to water is 0.01-0.5:10-50, and the mass ratio of the total mass of the ammonium molybdate and water to the anhydrous ethanol is 10-50:40-90.

6. The preparation method according to claim 4 or 5, characterized in that The ball milling speed is 400-1600 r / min, and the ball milling time is 12-48 h; the mass ratio of the total mass of the PVC resin, graphite powder and ammonium molybdate ethanol aqueous solution to the ball milling beads is 96-128:40-80.

7. The preparation method according to claim 4, characterized in that The drying temperature is 40-80°C and the holding time is 10-24 hours.

8. The preparation method according to claim 4, characterized in that The plasticizing temperature is 120-160° C., and the holding time is 6-14 minutes.

9. The preparation method according to claim 4, characterized in that The temperature of the hot pressing molding is 120-160° C., the pressure is 1-4 MPa, and the holding time is 2-10 min.

10. Use of the graphene / ammonium molybdate synergistically modified PVC composite material according to any one of claims 1 to 3 or the graphene / ammonium molybdate synergistically modified PVC composite material obtained by the preparation method according to any one of claims 4 to 9 in thermal and physical barriers.

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