Functionalized polystyrene infrared stealth film material and preparation method thereof

Abstract

The invention discloses an infrared stealth film material of functionalized polystyrene and a preparation method thereof, and belongs to the technical field of functional material preparation. The infrared stealth film material of functionalized polystyrene is composed of the following components in parts by weight: 53-67 parts of a base film material, 8-12 parts of modified polystyrene, and 0.8-1.3 parts of an adhesive, wherein the base film material is prepared from meta-iodoaniline, trimethylsilyl acetylene, diisopropyl xanthate disulfide, tetramethylammonium hydroxide, polyvinylidene fluoride, and polymethyl methacrylate, and the modified polystyrene is prepared from syringaldehyde, n-butyl bromide, 2,2'-dipyrrolyl methane, 2-thiophene boric acid, and polystyrene cross-linked microspheres. The infrared stealth film material of functionalized polystyrene prepared by the method has excellent stealth performance and mechanical properties.

Description

Technical Field

[0001] The invention belongs to the technical field of functional material preparation, and in particular relates to a functionalized polystyrene infrared stealth film material and a preparation method thereof. Background Art

[0002] With the rapid development of modern military technology, stealth technology plays a vital role in improving the survivability and combat effectiveness of weapons and equipment. Stealth technology is to reduce or change the observability of the target, increase the difficulty of enemy detection, tracking and identification, and thus greatly reduce the probability of being detected. Therefore, infrared stealth technology, as an important part of stealth technology, has received extensive attention and research. The core of infrared stealth technology is to reduce or change the infrared radiation characteristics of the target, making it difficult for infrared detection equipment to detect the target. As one of the key means to achieve this goal, infrared stealth film materials have important research significance. Polystyrene, as a common polymer material, has excellent physical and chemical properties, such as good processability, stability and low cost, making it an ideal substrate for preparing infrared stealth film. However, single polystyrene material has obvious limitations in infrared stealth, such as low infrared reflectivity and high infrared emissivity. Therefore, polystyrene needs to be treated on the surface or structure to make it have better infrared stealth performance.

[0003] Patent CN 112125997 B discloses a functionalized polystyrene microsphere and an infrared stealth anti-glare film material. The material comprises a polymer film and functionalized polystyrene microspheres fixed on the surface of the polymer film by an adhesive. The outer layer of the functionalized polystyrene microspheres is wrapped with a metal layer, has high infrared reflectivity and low infrared emissivity, and the infrared stealth anti-glare film material prepared therefrom has low infrared emissivity and no glare phenomenon, and can be used as infrared stealth for night combat personnel, armor, and vehicles. However, the stealth performance of the infrared stealth film material prepared by this method and the mechanical properties of the material still have room for improvement. Summary of the invention

[0004] The object of the present invention is to provide a functionalized polystyrene infrared stealth film material and a preparation method thereof, so as to solve the technical problems of poor stealth performance and mechanical properties of infrared stealth film materials in the prior art.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The invention provides an infrared stealth film material of functionalized polystyrene, which is composed of the following components in parts by weight: 53-67 parts of a base film material, 8-12 parts of modified polystyrene, and 0.8-1.3 parts of an adhesive, wherein the base film material is prepared from meta-iodoaniline, trimethylsilyl acetylene, diisopropyl xanthate disulfide, tetramethylammonium hydroxide, polyvinylidene fluoride and polymethyl methacrylate, and the modified polystyrene is prepared from syringaldehyde, n-butyl bromide, 2,2'-dipyrrolyl methane, 2-thiophene boric acid and polystyrene cross-linked microspheres.

[0007] Preferably, the method for preparing the substrate film material comprises the following steps:

[0008] Q1: Add m-iodoaniline, bis(triphenylphosphine)palladium dichloride and cuprous iodide into a container, evacuate and introduce nitrogen, then add 1,8-diazacyclo[5,4,0]undecene-7, acetonitrile, trimethylsilylacetylene and deionized water, seal the container, heat to react, cool after the reaction, pour the reactant into deionized water, extract, dry the organic layer, rotary evaporate, and recrystallize to obtain intermediate 1;

[0009] Q2: Add the intermediate product 1, azobisisobutyronitrile and diisopropyl xanthate disulfide into a container, introduce nitrogen, add m-xylene, stir, heat to react, cool after the reaction, purify to obtain the intermediate product 2;

[0010] Q3: Add the intermediate product 2 to a container, add a mixed solution of tetrahydrofuran and methanol under a nitrogen atmosphere, dissolve tetramethylammonium hydroxide in methanol and add it to the container, stir to react, add hydrated nickel chloride, continue the reaction, then add iodine to react, filter after the reaction, dissolve the solid crude product, add methanol dropwise, let stand, precipitate, wash, and obtain product 3;

[0011] Q4: Add polyvinylidene fluoride and polymethyl methacrylate to acetone, heat and stir, then add product 3 and deionized water and continue stirring, then pour into a container and dry to obtain a base film material.

[0012] In the above process, the synthetic reaction formula of product 3 is as follows:

[0013]

[0014] The results of mass spectrometry analysis were: m / z: 602.02 (100.0%), 604.02 (57.1%), 603.03 (30.6%), 605.02 (21.3%), 606.02 (8.0%), 606.01 (7.0%), 604.03 (5.5%), 607.02 (4.7%), 603.02 (4.7%), 606.03 (2.6%), 608.02 (2.2%), 608.01 (1.5%).

[0015] Preferably, in Q1, the molar ratio of m-iodoaniline, bis(triphenylphosphine)palladium dichloride, cuprous iodide and trimethylsilyl acetylene is (30-45): (0.3-0.45): (1-1.5): (15-22.5), the heating reaction temperature is 70-75°C, the time is 40-50h, the extraction is carried out with ethyl acetate, and the extraction is carried out with magnesium sulfate; in Q2, the molar ratio of the intermediate product 1, azobisisobutyronitrile and diisopropylxanthate disulfide is (1-2): (0.45-0.9): (1-2), the heating reaction temperature is 120-130°C, and the time is 20-24h.

[0016] Preferably, in Q3, the molar ratio of the intermediate product 2, tetramethylammonium hydroxide, hydrated nickel chloride and iodine is (2-4): (2.2-4.4): (1-2): (1-2), the stirring reaction time is 30-45 min, the continued reaction time is 10-12 h, and the reaction time is 10-12 h; in Q4, the amount ratio of polyvinylidene fluoride, polymethyl methacrylate, acetone and product 3 is (3.7-7.4) g: (1-2) g: (56-112) mL: (1-3) g, the heating and stirring temperature is 30-40°C, the time is 1-2 h, and the continued stirring time is 0.5-1.5 h.

[0017] Preferably, the method for preparing the modified polystyrene comprises the following steps:

[0018] S1: adding syringaldehyde to a container containing dimethyl sulfoxide, introducing nitrogen, adding potassium iodide and potassium carbonate under heating conditions to react, then adding n-butyl bromide to continue the reaction to obtain a crude product, diluting, extracting, washing, combining the organic phases, and drying to obtain compound A;

[0019] S2: Compound A and 2,2'-dipyrrolylmethane are added to dichloromethane, nitrogen is introduced, trifluoroacetic acid is added, and after reaction at room temperature, dichlorodicyanobenzoquinone is added, the reaction is continued, triethylamine is added to quench the reaction, and the mixture is purified to obtain compound B; Compound B is added to chloroform containing pyridine, N-bromosuccinimide is added under low temperature, the reaction is stirred, acetone is used to quench the reaction, and the mixture is purified to obtain compound C;

[0020] S3: adding compound C, 2-thiopheneboric acid, tetrakis(triphenylphosphine)palladium and cesium carbonate to a mixed solution of toluene and N,N-dimethylformamide, introducing nitrogen, heating under reflux for reaction, cooling, reducing pressure, washing, drying and purifying after the reaction is completed to obtain compound D;

[0021] S4: Add polystyrene cross-linked microspheres and dichloromethane into a container, swell, then add compound D and anhydrous tin tetrachloride, react at room temperature, add dilute hydrochloric acid, filter, wash, and vacuum dry to obtain modified polystyrene.

[0022] In the above process, the synthetic reaction formula of compound D is as follows:

[0023]

[0024] The results of mass spectrometry analysis were: m / z: 892.33 (100.0%), 893.34 (57.1%), 894.34 (18.1%), 894.33 (9.9%), 895.33 (5.4%), 895.34 (4.0%), 893.33 (3.1%), 896.34 (1.8%).

[0025] Preferably, in S1, the molar ratio of syringaldehyde, potassium iodide, potassium carbonate and n-butane bromide is (10-12): (0.06-0.072): (16.16-19.39): (10.3-12.36), the heating temperature is 80-90°C, the reaction time is 30-45min, the reaction time is continued for 3-4h, diluted with distilled water, extracted with dichloromethane, washed with 2mol / L sodium hydroxide solution, and dried with anhydrous sodium sulfate.

[0026] Preferably, in S2, the molar ratio of compound A, 2,2'-dipyrrolylmethane, trifluoroacetic acid and dichlorodicyanobenzoquinone is (1-1.3): (1-1.3): (0.65-0.85): (1.29-1.68), and the reaction time is 3-5h; the molar ratio of compound B and N-bromosuccinimide is (1-2): (2-4), the low temperature is 0-1°C, and the stirring reaction time is 30-45min.

[0027] Preferably, in S3, the molar ratio of compound C, 2-thiopheneboric acid, tetrakis(triphenylphosphine)palladium and cesium carbonate is (1-2):(1-2):(0.1-0.2):(4.5-9.1), the heating reflux temperature is 80-90°C, and the time is 8-10h; in S4, the amount ratio of polystyrene cross-linked microspheres, dichloromethane, compound D and anhydrous tin tetrachloride is (3-6) g:(30-60) mL:(2-4) g:(1.1-1.5) mL, the cross-linking degree of the polystyrene cross-linked microspheres is 4.5%, the particle size is 0.32-0.45 mm, the room temperature reaction is 40-50h, and the concentration of dilute hydrochloric acid is 1 mol / L.

[0028] Preferably, the method for preparing the functionalized polystyrene infrared stealth film material comprises the following steps:

[0029] Step (1): mixing the adhesive and the modified polystyrene to prepare a mixed solution;

[0030] Step (2): spray the mixed liquid evenly on the surface of the base film material, and dry it to obtain an infrared stealth film material of functionalized polystyrene.

[0031] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0032] 1. The present invention first uses meta-iodoaniline, trimethylsilyl acetylene, tetramethylammonium hydroxide, polyvinylidene fluoride and polymethyl methacrylate as raw materials to prepare a base film material, and then uses syringaldehyde, n-butyl bromide, 2,2'-dipyrrolyl methane, 2-thiophene boronic acid and polystyrene cross-linked microspheres to prepare modified polystyrene, and the obtained modified polystyrene is evenly sprayed into the base film material through an adhesive, so that the obtained infrared stealth film material has excellent stealth performance and mechanical properties.

[0033] 2. The present invention utilizes meta-iodoaniline, trimethylsilyl acetylene, tetramethylammonium hydroxide, polyvinylidene fluoride and polymethyl methacrylate as raw materials to prepare a base film material. The obtained base film material is used in an infrared stealth film material to effectively enhance its infrared stealth performance. The obtained product 3 has a specific molecular structure and electronic arrangement so that it has a lower reflectivity in the infrared spectrum region, reducing the visibility of the material under an infrared detector. Polyvinylidene fluoride and polymethyl methacrylate serve as polymer matrices, and their molecular chain structure enables them to effectively transfer and disperse stress when subjected to external forces, thereby improving the mechanical properties of the base film material.

[0034] 3. The present invention uses syringaldehyde, n-butyl bromide, 2,2'-dipyrrolylmethane, 2-thiopheneboronic acid and polystyrene cross-linked microspheres to prepare modified polystyrene. The electron cloud distribution and electron vibration mode in the thiophene group and porphyrin structure contained in the prepared compound D make it have a specific absorption peak in the infrared spectrum region. When infrared radiation irradiates the surface of the material, the groups contained can absorb the energy of infrared photons and convert them into heat energy or other forms of energy dissipation, thereby significantly reducing the visibility of the material under infrared detectors; the network structure of the polystyrene cross-linked microspheres contained provides good mechanical support for the modified polystyrene, improving the overall mechanical properties. DETAILED DESCRIPTION

[0035] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] Embodiment 1: This embodiment discloses a method for preparing a substrate film material, comprising the following steps:

[0037] Q1: 8.22 g of m-iodoaniline, 0.27 g of bis(triphenylphosphine)palladium dichloride and 0.24 g of cuprous iodide were added to a container, and nitrogen was introduced after vacuuming. Then, 24 mL of 1,8-diazacyclo[5,4,0]undecene-7, 80 mL of acetonitrile, 2.65 mL of trimethylsilylacetylene and 0.44 mL of deionized water were added. After sealing the container, the reaction was heated to 75°C for 48 h. After the reaction was completed, the reaction was cooled, the reactants were poured into deionized water, extracted with ethyl acetate, and the organic layer was dried with magnesium sulfate, rotary evaporated, and recrystallized to obtain intermediate 1;

[0038] Q2: 0.32 g of intermediate product 1, 0.11 g of azobisisobutyronitrile and 0.41 g of diisopropyl xanthate disulfide were added to a container, nitrogen was introduced, and 100 mL of m-xylene was added, stirred, and reacted at 125° C. for 24 h. After the reaction was completed, the mixture was cooled and purified to obtain intermediate product 2;

[0039] Q3: 0.27 g of intermediate product 2 was added to a container. Under a nitrogen atmosphere, a mixed solution of 2 mL of tetrahydrofuran and 1.5 mL of methanol was added. 0.18 g of tetramethylammonium hydroxide was dissolved in 0.5 mL of methanol and added to the container. After stirring for 45 min, 0.11 g of hydrated nickel chloride was added and the reaction was continued for 12 h. Subsequently, 0.11 g of iodine was added and the reaction was continued for 12 h. After the reaction was completed, the solid crude product was filtered and dissolved. Methanol was added dropwise. The mixture was allowed to stand for precipitation and washed to obtain product 3.

[0040] Q4: Add 5.55 g of polyvinylidene fluoride and 1.5 g of polymethyl methacrylate into 84 mL of acetone, heat to 40 °C and stir for 2 h, then add 2 g of product 3 and 2.5 mL of deionized water and continue stirring for 1.5 h. Subsequently, pour into a container and dry to obtain a base film material.

[0041] This embodiment discloses a method for preparing modified polystyrene, comprising the following steps:

[0042] S1: 11.49 g of syringaldehyde was added to a container containing 60 mL of dimethyl sulfoxide, nitrogen was introduced, and the mixture was heated to 85°C. Then, 0.066 g of potassium iodide and 14.74 g of potassium carbonate were added to react for 45 min, and then 9.4 g of n-butyl bromide was added to continue the reaction for 4 h to obtain a crude product, which was diluted with distilled water, extracted with dichloromethane, washed with 2 mol / L sodium hydroxide solution, and the organic phases were combined and dried with anhydrous sodium sulfate to obtain compound A;

[0043] S2: 0.58 g of compound A and 0.93 g of 2,2'-dipyrrolyl methane were added to 600 mL of dichloromethane, nitrogen was introduced, 0.19 mL of trifluoroacetic acid was added, and the mixture was reacted at room temperature for 3 h. Then, 1.15 g of dichlorodicyanobenzoquinone was added, and the reaction was continued for 1 h. Triethylamine was added to quench the reaction, and the mixture was purified to obtain compound B. 5.45 g of compound B was added to 400 mL of chloroform dissolved with 4 mL of pyridine, and 2.67 g of N-bromosuccinimide was added at 0°C. After stirring for 45 min, the reaction was quenched with acetone, and the mixture was purified to obtain compound C.

[0044] S3: 0.66 g of compound C, 0.093 g of 2-thiopheneboric acid, 0.087 g of tetrakis(triphenylphosphine)palladium and 1.31 g of cesium carbonate were added to a mixed solution of 20 mL of toluene and 5 mL of N,N-dimethylformamide, nitrogen was introduced, and the mixture was refluxed at 85° C. for 10 h. After the reaction was completed, the mixture was cooled, decompressed, washed, dried and purified to obtain compound D;

[0045] S4: Add 4.5 g of polystyrene cross-linked microspheres with a cross-linking degree of 4.5% and a particle size of 0.32-0.45 mm and 45 mL of dichloromethane into a container and allow to swell. Then add 3 g of compound D and 1.3 mL of anhydrous tin tetrachloride. After reacting at room temperature for 48 h, add 10 mL of 1 mol / L dilute hydrochloric acid, filter, wash, and vacuum dry to obtain modified polystyrene.

[0046] This embodiment discloses a functionalized polystyrene infrared stealth film material, which is composed of the following components in parts by weight: 60 parts of base film material, 10 parts of modified polystyrene, and 1.05 parts of acrylic resin.

[0047] This embodiment discloses a method for preparing a functionalized polystyrene infrared stealth film material, comprising the following steps:

[0048] Step (1): mixing acrylic resin and modified polystyrene to prepare a mixed solution;

[0049] Step (2): spray the mixed liquid evenly on the surface of the base film material, and dry it to obtain an infrared stealth film material of functionalized polystyrene.

[0050] Embodiment 2: This embodiment discloses a method for preparing a substrate film material, comprising the following steps:

[0051] Q1: 6.57 g of m-iodoaniline, 0.21 g of bis(triphenylphosphine)palladium dichloride and 0.29 g of cuprous iodide were added to a container, and nitrogen was introduced after vacuuming. Then, 24 mL of 1,8-diazacyclo[5,4,0]undecene-7, 80 mL of acetonitrile, 2.12 mL of trimethylsilylacetylene and 0.44 mL of deionized water were added. After sealing the container, the reaction was heated to 75°C for 48 hours. After the reaction was completed, the reaction was cooled, and the reactants were poured into deionized water, extracted with ethyl acetate, and the organic layer was dried with magnesium sulfate, rotary evaporated, and recrystallized to obtain intermediate 1;

[0052] Q2: 0.21 g of intermediate product 1, 0.07 g of azobisisobutyronitrile and 0.54 g of diisopropyl xanthate disulfide were added to a container, nitrogen was introduced, and 100 mL of m-xylene was added, stirred, and reacted at 125°C for 24 h. After the reaction was completed, the mixture was cooled and purified to obtain intermediate product 2;

[0053] Q3: 0.18 g of intermediate product 2 was added to a container. Under a nitrogen atmosphere, a mixed solution of 2 mL of tetrahydrofuran and 1.5 mL of methanol was added. 0.24 g of tetramethylammonium hydroxide was dissolved in 0.5 mL of methanol and added to the container. After stirring for 45 min, 0.07 g of hydrated nickel chloride was added and the reaction was continued for 12 h. Subsequently, 0.07 g of iodine was added and the reaction was continued for 12 h. After the reaction was completed, the solid crude product was filtered and dissolved. Methanol was added dropwise. The mixture was allowed to stand for precipitation and washed to obtain product 3.

[0054] Q4: Add 3.7 g of polyvinylidene fluoride and 1 g of polymethyl methacrylate into 112 mL of acetone, heat to 40 °C and stir for 2 h, then add 1 g of product 3 and 2.5 mL of deionized water and continue stirring for 1.5 h. Subsequently, pour into a container and dry to obtain a base film material.

[0055] This embodiment discloses a method for preparing modified polystyrene, comprising the following steps:

[0056] S1: 10.44 g of syringaldehyde was added to a container containing 60 mL of dimethyl sulfoxide, nitrogen was introduced, and the mixture was heated to 85°C. Then, 0.06 g of potassium iodide and 13.4 g of potassium carbonate were added and the mixture was reacted for 45 min. Then, 10.2 g of n-butyl bromide was added and the reaction was continued for 4 h to obtain a crude product, which was diluted with distilled water, extracted with dichloromethane, washed with 2 mol / L sodium hydroxide solution, and the organic phases were combined and dried with anhydrous sodium sulfate to obtain compound A;

[0057] S2: Add 0.5 g of compound A and 0.81 g of 2,2'-dipyrrolylmethane to 600 mL of dichloromethane, add 0.165 mL of trifluoroacetic acid after nitrogen is introduced, react at room temperature for 3 h, add 1.3 g of dichlorodicyanobenzoquinone, continue to react for 1 h, add triethylamine to quench the reaction, purify to obtain compound B; add 3.63 g of compound B to 400 mL of chloroform dissolved with 4 mL of pyridine, add 1.78 g of N-bromosuccinimide at 0°C, stir to react for 45 min, quench the reaction with acetone, purify to obtain compound C;

[0058] S3: 0.44 g of compound C, 0.062 g of 2-thiopheneboric acid, 0.058 g of tetrakis(triphenylphosphine)palladium and 0.87 g of cesium carbonate were added to a mixed solution of 20 mL of toluene and 5 mL of N,N-dimethylformamide, and nitrogen was introduced, and the mixture was refluxed at 85° C. for 10 h. After the reaction was completed, the mixture was cooled, decompressed, washed, dried and purified to obtain compound D;

[0059] S4: 3 g of polystyrene cross-linked microspheres with a cross-linking degree of 4.5% and a particle size of 0.40 mm and 60 mL of dichloromethane were added to a container for swelling, and then 4 g of compound D and 1.1 mL of anhydrous tin tetrachloride were added. After reacting at room temperature for 48 h, 10 mL of 1 mol / L dilute hydrochloric acid was added, filtered, washed, and vacuum dried to obtain modified polystyrene.

[0060] This embodiment discloses a functionalized polystyrene infrared stealth film material, which is composed of the following components in parts by weight: 53 parts of a base film material, 12 parts of modified polystyrene, and 1.3 parts of an acrylic resin.

[0061] This embodiment discloses a method for preparing a functionalized polystyrene infrared stealth film material, comprising the following steps:

[0062] Step (1): mixing acrylic resin and modified polystyrene to prepare a mixed solution;

[0063] Step (2): spray the mixed liquid evenly on the surface of the base film material, and dry it to obtain an infrared stealth film material of functionalized polystyrene.

[0064] Embodiment 3: This embodiment discloses a method for preparing a substrate film material, comprising the following steps:

[0065] Q1: 9.86 g of m-iodoaniline, 0.32 g of bis(triphenylphosphine)palladium dichloride and 0.19 g of cuprous iodide were added to a container, and nitrogen was introduced after vacuuming. Then, 24 mL of 1,8-diazacyclo[5,4,0]undecene-7, 80 mL of acetonitrile, 3.18 mL of trimethylsilylacetylene and 0.44 mL of deionized water were added. After sealing the container, the reaction was heated to 75°C for 48 h. After the reaction was completed, the reaction was cooled, and the reactants were poured into deionized water, extracted with ethyl acetate, and the organic layer was dried with magnesium sulfate, rotary evaporated, and recrystallized to obtain intermediate 1;

[0066] Q2: 0.42 g of intermediate product 1, 0.14 g of azobisisobutyronitrile and 0.27 g of diisopropyl xanthate disulfide were added to a container, nitrogen was introduced, and 100 mL of m-xylene was added, stirred, and reacted at 125° C. for 24 h. After the reaction was completed, the mixture was cooled and purified to obtain intermediate product 2;

[0067] Q3: 0.36 g of intermediate product 2 was added to a container. Under a nitrogen atmosphere, a mixed solution of 2 mL of tetrahydrofuran and 1.5 mL of methanol was added. 0.12 g of tetramethylammonium hydroxide was dissolved in 0.5 mL of methanol and added to the container. After stirring for 45 min, 0.14 g of hydrated nickel chloride was added and the reaction was continued for 12 h. Subsequently, 0.09 g of iodine was added and the reaction was continued for 12 h. After the reaction was completed, the solid crude product was filtered and dissolved. Methanol was added dropwise. The mixture was allowed to stand for precipitation and washed to obtain product 3.

[0068] Q4: Add 7.4 g of polyvinylidene fluoride and 2 g of polymethyl methacrylate into 56 mL of acetone, heat to 40 °C and stir for 2 h, then add 3 g of product 3 and 2.5 mL of deionized water and continue stirring for 1.5 h. Subsequently, pour into a container and dry to obtain a base film material.

[0069] This embodiment discloses a method for preparing modified polystyrene, comprising the following steps:

[0070] S1: 12.53 g of syringaldehyde was added to a container containing 60 mL of dimethyl sulfoxide, nitrogen was introduced, and the mixture was heated to 85°C. Then, 0.072 g of potassium iodide and 16.08 g of potassium carbonate were added to react for 45 min, and then 8.5 g of n-butyl bromide was added to continue the reaction for 4 h to obtain a crude product, which was diluted with distilled water, extracted with dichloromethane, washed with 2 mol / L sodium hydroxide solution, and the organic phases were combined and dried with anhydrous sodium sulfate to obtain compound A;

[0071] S2: 0.65 g of compound A and 1.05 g of 2,2'-dipyrrolyl methane were added to 600 mL of dichloromethane, nitrogen was introduced, 0.215 mL of trifluoroacetic acid was added, and the mixture was reacted at room temperature for 3 h. Then, 1 g of dichlorodicyanobenzoquinone was added, and the reaction was continued for 1 h. Triethylamine was added to quench the reaction, and the mixture was purified to obtain compound B. 7.26 g of compound B was added to 400 mL of chloroform dissolved with 4 mL of pyridine, and 3.56 g of N-bromosuccinimide was added at 0°C. After stirring for 45 min, the reaction was quenched with acetone, and the mixture was purified to obtain compound C.

[0072] S3: 0.88 g of compound C, 0.124 g of 2-thiopheneboric acid, 0.116 g of tetrakis(triphenylphosphine)palladium and 1.74 g of cesium carbonate were added to a mixed solution of 20 mL of toluene and 5 mL of N,N-dimethylformamide, nitrogen was introduced, and the mixture was refluxed at 85° C. for 10 h. After the reaction was completed, the mixture was cooled, decompressed, washed, dried and purified to obtain compound D;

[0073] S4: 6 g of polystyrene cross-linked microspheres with a cross-linking degree of 4.5% and a particle size of 0.40 mm and 30 mL of dichloromethane were added to a container and allowed to swell. Then, 2 g of compound D and 1.5 mL of anhydrous tin tetrachloride were added. After reacting at room temperature for 48 h, 10 mL of 1 mol / L dilute hydrochloric acid was added. The mixture was filtered, washed, and vacuum dried to obtain modified polystyrene.

[0074] This embodiment discloses a functionalized polystyrene infrared stealth film material, which is composed of the following components in parts by weight: 67 parts of base film material, 8 parts of modified polystyrene, and 0.8 parts of acrylic resin.

[0075] This embodiment discloses a method for preparing a functionalized polystyrene infrared stealth film material, comprising the following steps:

[0076] Step (1): mixing acrylic resin and modified polystyrene to prepare a mixed solution;

[0077] Step (2): spray the mixed liquid evenly on the surface of the base film material, and dry it to obtain an infrared stealth film material of functionalized polystyrene.

[0078] Embodiment 4: This embodiment discloses a method for preparing a substrate film material, comprising the following steps:

[0079] Q1: 7.4 g of m-iodoaniline, 0.24 g of bis(triphenylphosphine)palladium dichloride and 0.26 g of cuprous iodide were added to a container, and nitrogen was introduced after vacuuming. Then, 24 mL of 1,8-diazacyclo[5,4,0]undecene-7, 80 mL of acetonitrile, 2.92 mL of trimethylsilylacetylene and 0.44 mL of deionized water were added. After sealing the container, the reaction was heated to 75°C for 48 h. After the reaction was completed, the reaction was cooled, and the reactants were poured into deionized water, extracted with ethyl acetate, and the organic layer was dried with magnesium sulfate, rotary evaporated, and recrystallized to obtain intermediate 1;

[0080] Q2: 0.27 g of intermediate product 1, 0.13 g of azobisisobutyronitrile and 0.34 g of diisopropyl xanthate disulfide were added to a container, nitrogen was introduced, and 100 mL of m-xylene was added, stirred, and reacted at 125° C. for 24 h. After the reaction was completed, the mixture was cooled and purified to obtain intermediate product 2;

[0081] Q3: 0.23 g of intermediate product 2 was added to a container. Under a nitrogen atmosphere, a mixed solution of 2 mL of tetrahydrofuran and 1.5 mL of methanol was added. 0.15 g of tetramethylammonium hydroxide was dissolved in 0.5 mL of methanol and added to the container. After stirring for 45 min, 0.09 g of hydrated nickel chloride was added and the reaction was continued for 12 h. Subsequently, 0.13 g of iodine was added and the reaction was continued for 12 h. After the reaction was completed, the solid crude product was filtered and dissolved. Methanol was added dropwise. The mixture was allowed to stand for precipitation and washed to obtain product 3.

[0082] Q4: Add 4.63 g of polyvinylidene fluoride and 1.7 g of polymethyl methacrylate into 70 mL of acetone, heat to 40 °C and stir for 2 h, then add 1.5 g of product 3 and 2.5 mL of deionized water and continue stirring for 1.5 h. Subsequently, pour into a container and dry to obtain a base film material.

[0083] This embodiment discloses a method for preparing modified polystyrene, comprising the following steps:

[0084] S1: 10.97 g of syringaldehyde was added to a container containing 60 mL of dimethyl sulfoxide, nitrogen was introduced, and the mixture was heated to 85°C. Then, 0.063 g of potassium iodide and 15.41 g of potassium carbonate were added to react for 45 min, and then 8.95 g of n-butyl bromide was added to continue the reaction for 4 h to obtain a crude product, which was diluted with distilled water, extracted with dichloromethane, washed with 2 mol / L sodium hydroxide solution, and the organic phases were combined and dried with anhydrous sodium sulfate to obtain compound A;

[0085] S2: 0.54 g of compound A and 0.87 g of 2,2'-dipyrrolyl methane were added to 600 mL of dichloromethane, nitrogen was introduced, 0.178 mL of trifluoroacetic acid was added, and the mixture was reacted at room temperature for 3 h. 1.1 g of dichlorodicyanobenzoquinone was added, and the reaction was continued for 1 h. Triethylamine was added to quench the reaction, and the mixture was purified to obtain compound B; 6.36 g of compound B was added to 400 mL of chloroform dissolved with 4 mL of pyridine, 2.23 g of N-bromosuccinimide was added at 0°C, the mixture was stirred for reaction for 45 min, the reaction was quenched with acetone, and the mixture was purified to obtain compound C;

[0086] S3: 0.55 g of compound C, 0.078 g of 2-thiopheneboric acid, 0.073 g of tetrakis(triphenylphosphine)palladium and 1.09 g of cesium carbonate were added to a mixed solution of 20 mL of toluene and 5 mL of N,N-dimethylformamide, nitrogen was introduced, and the mixture was refluxed at 85° C. for 10 h. After the reaction was completed, the mixture was cooled, decompressed, washed, dried and purified to obtain compound D;

[0087] S4: 4 g of polystyrene cross-linked microspheres with a cross-linking degree of 4.5% and a particle size of 0.38 mm and 40 mL of dichloromethane were added to a container for swelling, and then 2.5 g of compound D and 1.2 mL of anhydrous tin tetrachloride were added. After reacting at room temperature for 48 hours, 10 mL of 1 mol / L dilute hydrochloric acid was added, filtered, washed, and vacuum dried to obtain modified polystyrene.

[0088] This embodiment discloses a functionalized polystyrene infrared stealth film material, which is composed of the following components in parts by weight: 58 parts of base film material, 11 parts of modified polystyrene, and 0.9 parts of acrylic resin.

[0089] This embodiment discloses a method for preparing a functionalized polystyrene infrared stealth film material, comprising the following steps:

[0090] Step (1): mixing acrylic resin and modified polystyrene to prepare a mixed solution;

[0091] Step (2): spray the mixed liquid evenly on the surface of the base film material, and dry it to obtain an infrared stealth film material of functionalized polystyrene.

[0092] Comparative Example 1: Compared with Example 1, in the process of preparing the base film material in Comparative Example 1, diisopropyl xanthate disulfide is not added, and other conditions remain unchanged.

[0093] Comparative Example 2: Compared with Example 1, in the process of preparing modified polystyrene in Comparative Example 2, 2-thiopheneboric acid is not added, and other conditions remain unchanged.

[0094] Comparative Example 3: Compared with Example 1, in the process of preparing the infrared stealth film material of functionalized polystyrene, Comparative Example 3 uses polyvinylidene fluoride instead of the base film material, and other conditions remain unchanged.

[0095] Comparative Example 4: Compared with Example 1, in Comparative Example 4, in the process of preparing the infrared stealth film material of functionalized polystyrene, polystyrene cross-linked microspheres are used instead of modified polystyrene, and other conditions remain unchanged.

[0096] Experimental example: The prepared samples were subjected to performance tests. The infrared emissivity of the samples in the 8μm-14μm band was measured according to GJB 8700-2015. The lower the infrared emissivity, the better the infrared stealth effect. The tensile strength of the samples was measured according to GB / T 1040.1-2018. The test results are shown in Table 1:

[0097] Table 1

[0098] project Infrared radiation rate / % Tensile strength / MPa Example 1 0.15 68.56 Example 2 0.16 68.12 Example 3 0.16 67.53 Example 4 0.17 67.03 Comparative Example 1 0.28 59.73 Comparative Example 2 0.29 58.79 Comparative Example 3 0.33 56.67 Comparative Example 4 0.36 56.34

[0099] It can be seen from the test results in Table 1 that the infrared stealth film materials prepared in Examples 1-4 of the present invention have excellent stealth performance and mechanical properties. By comparing Comparative Example 1 with Examples 1-4, it can be seen that the addition of diisopropyl xanthate disulfide can effectively improve the stealth performance and mechanical properties of the infrared stealth film material; by comparing Comparative Example 2 with Examples 1-4, it can be seen that the addition of 2-thiophene boronic acid can effectively improve the stealth performance and mechanical properties of the infrared stealth film material; by comparing Comparative Example 3 with Examples 1-4, it can be seen that the presence of the base film material can effectively improve the stealth performance and mechanical properties of the infrared stealth film material; by comparing Comparative Example 4 with Examples 1-4, it can be seen that the presence of modified polystyrene can effectively improve the stealth performance and mechanical properties of the infrared stealth film material.

[0100] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0101] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. Functionalized polystyrene infrared stealth film material, characterized in that: The invention is composed of the following components in parts by weight: 53-67 parts of a base film material, 8-12 parts of modified polystyrene, and 0.8-1.3 parts of an adhesive, wherein the base film material is prepared from meta-iodoaniline, trimethylsilyl acetylene, diisopropyl xanthate disulfide, tetramethylammonium hydroxide, polyvinylidene fluoride, and polymethyl methacrylate, and the modified polystyrene is prepared from syringaldehyde, n-butyl bromide, 2,2'-dipyrrolyl methane, 2-thiophene boric acid, and polystyrene cross-linked microspheres; The method for preparing the substrate film material comprises the following steps: Q1: Add m-iodoaniline, bis(triphenylphosphine)palladium dichloride and cuprous iodide into a container, evacuate and introduce nitrogen, then add 1,8-diazacyclo[5,4,0]undecene-7, acetonitrile, trimethylsilylacetylene and deionized water, seal the container, heat to react, cool after the reaction, pour the reactant into deionized water, extract, dry the organic layer, rotary evaporate, and recrystallize to obtain intermediate 1; Q2: Add the intermediate product 1, azobisisobutyronitrile and diisopropyl xanthate disulfide into a container, introduce nitrogen, add m-xylene, stir, heat to react, cool after the reaction, purify to obtain the intermediate product 2; Q3: Add the intermediate product 2 to a container, add a mixed solution of tetrahydrofuran and methanol under a nitrogen atmosphere, dissolve tetramethylammonium hydroxide in methanol and add it to the container, stir to react, add hydrated nickel chloride, continue the reaction, then add iodine to react, filter after the reaction, dissolve the solid crude product, add methanol dropwise, let stand, precipitate, wash, and obtain product 3; Q4: Add polyvinylidene fluoride and polymethyl methacrylate to acetone, heat and stir, then add product 3 and deionized water and continue stirring, then pour into a container and dry to obtain a base film material; The preparation method of the modified polystyrene comprises the following steps: S1: adding syringaldehyde to a container containing dimethyl sulfoxide, introducing nitrogen, adding potassium iodide and potassium carbonate under heating conditions to react, then adding n-butyl bromide to continue the reaction to obtain a crude product, diluting, extracting, washing, combining the organic phases, and drying to obtain compound A; S2: Compound A and 2,2'-dipyrrolylmethane are added to dichloromethane, nitrogen is introduced, trifluoroacetic acid is added, and after reaction at room temperature, dichlorodicyanobenzoquinone is added, the reaction is continued, triethylamine is added to quench the reaction, and the mixture is purified to obtain compound B; Compound B is added to chloroform containing pyridine, N-bromosuccinimide is added under low temperature, the reaction is stirred, acetone is used to quench the reaction, and the mixture is purified to obtain compound C; S3: adding compound C, 2-thiopheneboric acid, tetrakis(triphenylphosphine)palladium and cesium carbonate to a mixed solution of toluene and N,N-dimethylformamide, introducing nitrogen, heating under reflux for reaction, cooling, reducing pressure, washing, drying and purifying after the reaction is completed to obtain compound D; S4: Add polystyrene cross-linked microspheres and dichloromethane into a container, swell, then add compound D and anhydrous tin tetrachloride, react at room temperature, add dilute hydrochloric acid, filter, wash, and vacuum dry to obtain modified polystyrene.

2. The infrared stealth film material of functionalized polystyrene according to claim 1, characterized in that: In the Q1, the molar ratio of m-iodoaniline, bis(triphenylphosphine)palladium dichloride, cuprous iodide and trimethylsilyl acetylene is (30-45): (0.3-0.45): (1-1.5): (15-22.5), and the amount ratio of 1,8-diazacyclo[5,4,0]undecene-7, acetonitrile, trimethylsilyl acetylene and deionized water is 24 mL: (70-90) mL: (2.55-2.75) mL: (0.33-0.55) mL, the heating reaction temperature is 70-75°C, the time is 40-50h, extracted with ethyl acetate, and dried with magnesium sulfate; in Q2, the molar ratio of the intermediate product 1, azobisisobutyronitrile, diisopropyl xanthate disulfide and meta-xylene is (1-2) mol: (0.45-0.9) mol: (1-2) mol: (0.8-0.82) mmol, the heating reaction temperature is 120-130°C, and the time is 20-24h.

3. The infrared stealth film material of functionalized polystyrene according to claim 1, characterized in that: In Q3, the molar ratio of the intermediate product 2, tetramethylammonium hydroxide, hydrated nickel chloride and iodine is (2-4): (2.2-4.4): (1-2): (1-2), the volume ratio of tetrahydrofuran and methanol is 4:3, the stirring reaction time is 30-45 min, the continued reaction time is 10-12 h, and the reaction time is 10-12 h; in Q4, the amount ratio of polyvinylidene fluoride, polymethyl methacrylate, acetone, product 3 and deionized water is (3.7-7.4) g: (1-2) g: (56-112) mL: (1-3) g: (2-3) mL, the heating and stirring temperature is 30-40°C, the time is 1-2 h, and the continued stirring time is 0.5-1.5 h.

4. The infrared stealth film material of functionalized polystyrene according to claim 1, characterized in that: In the S1, the molar ratio of syringaldehyde, potassium iodide, potassium carbonate and n-butane bromide is (10-12): (0.06-0.072): (16.16-19.39): (10.3-12.36), the heating temperature is 80-90°C, the reaction time is 30-45min, the reaction time is continued for 3-4h, diluted with distilled water, extracted with dichloromethane, washed with 2mol / L sodium hydroxide solution, and dried with anhydrous sodium sulfate.

5. The infrared stealth film material of functionalized polystyrene according to claim 1, characterized in that: In S2, the molar ratio of compound A, 2,2'-dipyrrolylmethane, trifluoroacetic acid and dichlorodicyanobenzoquinone is (1-1.3): (1-1.3): (0.65-0.85): (1.29-1.68), and the reaction time is 3-5h; the molar ratio of compound B and N-bromosuccinimide is (1-2): (2-4), the low temperature is 0-1°C, and the stirring reaction time is 30-45min.

6. The infrared stealth film material of functionalized polystyrene according to claim 1, characterized in that: In S3, the molar ratio of compound C, 2-thiopheneboric acid, tetrakis(triphenylphosphine)palladium and cesium carbonate is (1-2): (1-2): (0.1-0.2): (4.5-9.1), the volume ratio of toluene and N,N-dimethylformamide is 4:1, the heating reflux temperature is 80-90°C, and the time is 8-10h; in S4, the amount ratio of polystyrene cross-linked microspheres, dichloromethane, compound D and anhydrous tin tetrachloride is (3-6) g: (30-60) mL: (2-4) g: (1.1-1.5) mL, the cross-linking degree of the polystyrene cross-linked microspheres is 4.5%, the particle size is 0.32-0.45 mm, the room temperature reaction is 40-50h, and the concentration of dilute hydrochloric acid is 1 mol / L.

7. The method for preparing the infrared stealth film material of functionalized polystyrene according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step (1): mixing the adhesive and the modified polystyrene to prepare a mixed solution; Step (2): spray the mixed liquid evenly on the surface of the base film material, and dry it to obtain an infrared stealth film material of functionalized polystyrene.

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