A long-chain alkyl polyarylamine composite material with fluorescent properties and its application

Abstract

Disclosed are a long-chain alkyl polyarylamine composite material with fluorescent properties and applications thereof. The composite material comprises a long-chain alkyl polyarylamine and a polyolefin in a mass ratio of 1:19-1000. The structural formula of the long-chain alkyl polyarylamine is shown in formula (I): #imgabs0#Formula (I); wherein R is an alkyl group with 5-12 carbon atoms, the weight-average molecular weight is 5000-136000 g / mol, and the PDI is 1.41-2.24. The composite material is prepared by blending the long-chain alkyl polyarylamine with the polyolefin, thereby solving the problem of poor dispersibility of the mixed fluorescent substance and the polyolefin. The obtained composite material has strong fluorescence intensity and can be potentially used in the fields of display, light transfer film, fluorescence positioning, etc.

Description

Technical Field

[0001] The invention belongs to the technical field of organic polymer composite materials, and in particular relates to a long-chain alkyl polyarylamine composite material with fluorescent properties and applications thereof. Background Art

[0002] Fluorescent materials refer to a class of materials that can convert incident light to generate converted light with a predetermined wavelength. They are widely used in display, light transfer film, and lighting fields.

[0003] Polyolefins are a typical general-purpose material, often used as matrix materials in display, light transfer film, and lighting applications. Due to their low cost, high chemical stability, excellent mechanical properties, and excellent processability, they have become a widely used material in daily life. However, they are not inherently luminescent. Currently, the method for preparing polyolefin-based luminescent materials generally involves adding substances with luminescent properties to polyolefins. For example, by physically mixing fluorescent substances with polyolefins, luminescent materials based on polyolefins can be prepared. However, the poor compatibility of fluorescent substances with polyolefins leads to uneven dispersion, which in turn affects the product's luminescent properties. There are also studies that introduce luminescent substances such as polycyclic aromatic hydrocarbons, quantum dots, or rare earth complexes into polyolefin molecular chains through chemical reactions. However, this method involves complex chemical reactions, often requiring expensive equipment and environmentally unfriendly solvents, resulting in complex operations and high production costs.

[0004] Therefore, how to avoid using chemical reactions to prepare polyolefin-based luminescent materials and obtain materials with strong luminescence intensity is an urgent problem to be solved. Summary of the Invention

[0005] In response to the above-mentioned deficiencies in the prior art, the present invention provides a long-chain alkyl polyarylamine composite material with fluorescent properties. The composite material is prepared by blending long-chain alkyl polyarylamine with polyolefin, which solves the problem of poor dispersion of the mixed fluorescent substance and polyolefin. The obtained composite material has strong fluorescence intensity and can be potentially used in display, light transfer film, fluorescence positioning and other fields.

[0006] The object of the present invention is to provide a long-chain alkyl polyarylamine composite material with fluorescent properties, comprising a long-chain alkyl polyarylamine and a polyolefin in a mass ratio of 1:19 to 1000, wherein the structural formula of the long-chain alkyl polyarylamine is shown in formula (I):

[0007] Formula (I);

[0008] Wherein, R is an alkyl group with 5 to 12 carbon atoms, the weight average molecular weight is 5000 to 136000 g / mol, and the PDI is 1.41 to 2.24.

[0009] In some embodiments of the present invention, the polyolefin is selected from at least one of polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyoctene, poly(4-methyl-1-pentene), and polyolefin elastomer.

[0010] In some embodiments of the present invention, R is pentyl, hexyl, octyl or dodecyl.

[0011] In some embodiments of the present invention, the mass ratio of the long-chain alkyl polyarylamine to the polyolefin is 1:49-199.

[0012] In some embodiments of the present invention, the structural formula of the long-chain alkyl polyarylamine is as shown in formula (II):

[0013] Formula (II);

[0014] Among them, the weight average molecular weight is 5000~135241g / mol, and the PDI is 1.41~2.02.

[0015] Another object of the present invention is to provide a method for preparing the long-chain alkyl polyarylamine composite material, comprising the following steps:

[0016] The long-chain alkyl polyarylamine is mixed with polyolefin, and the mixture is melt-extruded to obtain the long-chain alkyl polyarylamine composite material.

[0017] In some embodiments of the present invention, the temperature of the melt extrusion is 150-220°C.

[0018] Another object of the present invention is to provide a method for preparing the long-chain alkyl polyarylamine, comprising the following steps:

[0019] Under the action of palladium catalyst and auxiliary agent, alkyl substituted aniline and reacting with 4, 4'-dibromobiphenyl to obtain the long-chain alkyl polyarylamine.

[0020] In some embodiments of the present invention, the structure of the palladium catalyst is as shown in formula (III):

[0021] Formula (III);

[0022] wherein R1 and R2 are independently hydrogen, methyl, ethyl or isopropyl, and R1 and R2 are not hydrogen at the same time.

[0023] In some embodiments of the present invention, the auxiliary agent includes an organic base and a solvent.

[0024] In some embodiments of the present invention, the molar ratio of the alkyl-substituted aniline to 4,4'-dibromobiphenyl is 1:1.

[0025] In some embodiments of the present invention, the molar ratio of the palladium catalyst to 4, 4'-dibromobiphenyl is 0.005-0.02:1.

[0026] In some embodiments of the present invention, the reaction temperature is 100-120° C., and the reaction time is 12-36 hours.

[0027] In some embodiments of the present invention, the reaction further includes a post-processing step after completion.

[0028] In some embodiments of the present invention, the molar ratio of the 4,4'-dibromobiphenyl to the organic base is 1:2-4.

[0029] In some embodiments of the present invention, the organic base is potassium tert-butoxide.

[0030] In some embodiments of the present invention, the solvent is toluene.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The long-chain alkyl polyarylamine of the present invention is entangled with the long main chain of polyolefin through its long side chain and aromatic amine structure, thereby improving the dispersibility of the long-chain alkyl polyarylamine and polyolefin, solving the problem of poor dispersion of the mixture of fluorescent substance and polyolefin. The obtained composite material has strong fluorescence intensity and can be potentially used in the fields of display, light transfer film, fluorescence positioning, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a fluorescence image of the long-chain alkyl polyarylamine composite material prepared in Example 1; in the figure, 112-0.1% is the long-chain alkyl polyarylamine composite material of Example 15, 112-0.3% is the long-chain alkyl polyarylamine composite material of Example 16, 112-0.5% is the long-chain alkyl polyarylamine composite material of Example 17, 112-1% is the long-chain alkyl polyarylamine composite material of Example 18, 112-2% is the long-chain alkyl polyarylamine composite material of Example 19, and 112-5% is the long-chain alkyl polyarylamine composite material of Example 20. DETAILED DESCRIPTION

[0034] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the embodiments described 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 making creative efforts should fall within the scope of protection of the present invention.

[0035] All raw materials of the present invention can be obtained through commercial channels.

[0036] t -BuOK is potassium tert-butoxide;

[0037] PDI is the molecular weight distribution index;

[0038] The structure of the imidazolium salt ligand L1 is shown below:

[0039] ;

[0040] The structure of the imidazolium salt ligand L2 is shown below:

[0041] ;

[0042] The structure of the imidazolium salt ligand L3 is shown below:

[0043] ;

[0044] The structure of the imidazolium salt ligand L4 is shown below:

[0045] .

[0046] Example 1

[0047] This embodiment provides a palladium catalyst C1, the preparation method of which comprises the following steps:

[0048] Imidazole ligand L1 (1.0 mmol), potassium carbonate (10 mmol), and palladium dichloride (1.0 mmol) were added to 10 mL of N-methylimidazole and mixed at room temperature. The mixture was then heated to 80°C and stirred for 12 hours. After the reaction, the liquid was removed under reduced pressure, and the crude product was dissolved in 5 mL of dichloromethane. 20 mL of n-hexane was then added, and the resulting palladium complex precipitate was collected by filtration, washed with n-hexane (2×20 mL), and dried to obtain an off-white palladium catalyst powder C1 with a yield of 81%. The NMR C-H spectrum of palladium catalyst C1 is as follows:

[0049] 1 H NMR (400 MHz, CDCl3) δ 7.50 (td, J = 1.6, 0.8 Hz, 1H), 7.12-7.07(m, 5H), 7.00 (dd, J = 5.6, 1.7 Hz, 1H), 6.85-6.81 (m, 4H), 6.60 (s, 4H), 3.82 (s, 6H), 3.72 (d, J = 0.6 Hz, 3H), 2.31 (s, 12H), 2.26 (d, J = 0.7 Hz, 6H).

[0050] 13 C NMR (101 MHz, CDCl3) δ 162.02, 156.48, 133.58, 133.45, 133.24,130.79, 130.15, 129.44, 127.53, 122.13, 116.03, 103.07, 62.77, 55.35, 35.03,21.03, 18.14.

[0051] The structure of palladium catalyst C1 is shown below:

[0052] .

[0053] Example 2

[0054] This embodiment provides a palladium catalyst C2, the preparation method of which comprises the following steps:

[0055] Imidazole salt ligand L2 (1.0 mmol), potassium carbonate (8 mmol), and palladium dichloride (1.0 mmol) were added to 8 mL of N-methylimidazole and mixed at room temperature. The mixture was then heated to 70°C and stirred for 16 hours. After the reaction, the liquid was removed under reduced pressure, and the crude product was dissolved in 5 mL of dichloromethane. 20 mL of n-hexane was then added, and the resulting palladium complex precipitate was collected by filtration, washed with n-hexane (2×20 mL), and dried to obtain an off-white palladium catalyst powder C2 with a yield of 76%. The NMR C-H spectrum of palladium catalyst C2 is as follows:

[0056] 1 H NMR (400 MHz, CDCl3) δ 7.50 (tt, J = 1.4, 0.7 Hz, 1H), 7.13-7.08(m, 5H), 7.00 (dd, J = 5.6, 1.7 Hz, 1H), 6.87-6.80 (m, 8H), 6.79-6.73 (m,2H), 3.82 (s, 6H), 3.72 (t, J = 0.7 Hz, 3H), 2.50 (qd, J = 7.5, 0.9 Hz, 8H), 1.26 (t, J = 7.5 Hz, 12H).

[0057] 13C NMR (101 MHz, CDCl3) δ 162.02, 156.48, 141.57, 136.09, 130.79,129.44, 128.76, 127.53, 127.01, 122.13, 116.03, 103.07, 62.77, 55.35, 35.03,24.15, 14.23.

[0058] The structure of palladium catalyst C2 is shown below:

[0059] .

[0060] Example 3

[0061] This embodiment provides a palladium catalyst C3, the preparation method of which comprises the following steps:

[0062] Imidazole salt ligand L3 (1.0 mmol), potassium carbonate (12 mmol), and palladium dichloride (1.0 mmol) were added to 12 mL of N-methylimidazole and mixed at room temperature. The mixture was then heated to 90°C and stirred for 10 hours. After the reaction, the liquid was removed under reduced pressure, and the crude product was dissolved in 5 mL of dichloromethane. 20 mL of n-hexane was then added, and the resulting palladium complex precipitate was collected by filtration, washed with n-hexane (2×20 mL), and dried to obtain an off-white palladium catalyst powder C3 with a yield of 74%. The NMR C-H spectrum of palladium catalyst C3 is as follows:

[0063] 1 H NMR (400 MHz, CDCl3) δ 7.50 (tt, J = 1.5, 0.7 Hz, 1H), 7.12-7.08(m, 5H), 7.00 (dd, J = 5.6, 1.7 Hz, 1H), 6.94-6.90 (m, 4H), 6.85-6.81 (m,4H), 6.76 (dd, J = 8.8, 7.7 Hz, 2H), 3.82 (s, 6H), 3.72 (t, J = 0.7 Hz, 3H), 2.89 (hd, J = 6.8, 0.7 Hz, 4H), 1.28 (d, J = 6.9 Hz, 24H).

[0064] 13C NMR (101 MHz, CDCl3) δ 162.02, 156.48, 144.25, 141.09, 130.79,129.44, 127.53, 127.24, 126.60, 122.13, 116.03, 103.07, 62.77, 55.35, 35.03,28.88, 24.04.

[0065] The structure of palladium catalyst C3 is shown below:

[0066] .

[0067] Example 4

[0068] This embodiment provides a long-chain alkyl polyarylamine, the preparation method of which comprises the following steps:

[0069] 4-pentylaniline (0.5 mmol), 4, 4'-dibromobiphenyl (0.5 mmol), palladium catalyst C1 (0.01 mmol), t -BuOK (1.5 mmol) was added to a 20 mL reaction tube, and 1.5 mL of toluene was added. Under nitrogen protection, the temperature was raised to 110 °C and stirred for 24 h. The mixture was cooled to room temperature to obtain a gray-black liquid. The mixture was precipitated in 50 mL of methanol to precipitate a gray solid, which was filtered and dried. The mixture was added to a 20 mL reaction tube and filtered. The filtrate was collected and precipitated in 50 mL of methanol for washing. The filtrate was filtered and washed twice. The washing was repeated, filtered, and dried to obtain a light yellow solid with a yield of 73.6%. After testing, the weight-average molecular weight Mw was 35817 g / mol, the molecular weight distribution index PDI was 1.54, and the structure of the long-chain alkyl polyarylamine is shown below:

[0070] .

[0071] Example 5

[0072] This embodiment provides a long-chain alkyl polyarylamine, the preparation method of which comprises the following steps:

[0073] 4-Hexylaniline (0.5 mmol), 4, 4'-dibromobiphenyl (0.5 mmol), palladium catalyst C2 (0.01 mmol), t-BuOK (1.5 mmol) was added to a 20 mL reaction tube, and 1.5 mL of toluene was added. Under the protection of nitrogen, the temperature was raised to 110°C and stirred for 24 h. The mixture was cooled to room temperature to obtain a gray-black liquid. The mixture was precipitated in 50 mL of methanol to precipitate a gray solid, which was filtered and dried. The mixture was added to a 20 mL reaction tube and filtered. The filtrate was collected and precipitated in 50 mL of methanol for washing. The filtrate was filtered and washed twice. The washing was repeated, filtered, and dried to obtain a light yellow solid with a yield of 76.6%. After testing, the weight-average molecular weight Mw was 34415 g / mol, the molecular weight distribution index PDI was 2.08, and the structure of the long-chain alkyl polyarylamine is shown below:

[0074] .

[0075] Example 6

[0076] This embodiment provides a long-chain alkyl polyarylamine, the preparation method of which comprises the following steps:

[0077] 4-Octylaniline (1 mmol), 4, 4'-dibromobiphenyl (1 mmol), palladium catalyst C1 (0.01 mmol), t -BuOK (3 mmol) was added to a 20 mL reaction tube, and 1.5 mL of toluene was added. Under nitrogen protection, the temperature was raised to 110 °C and stirred for 24 h. The mixture was cooled to room temperature to obtain a gray-black liquid. The mixture was precipitated in 50 mL of methanol to precipitate a gray solid, which was filtered and dried. The mixture was added to a 20 mL reaction tube and filtered. The filtrate was collected and precipitated in 50 mL of methanol for washing. The filtrate was filtered and washed twice. The washing was repeated, filtered, and dried to obtain a light yellow solid with a yield of 65.4%. After testing, the weight-average molecular weight Mw was 92117 g / mol, the molecular weight distribution index PDI was 2.24, and the structure of the long-chain alkyl polyarylamine is shown below:

[0078] .

[0079] Example 7

[0080] This embodiment provides a long-chain alkyl polyarylamine, the preparation method of which comprises the following steps:

[0081] 4-Dodecylaniline (1 mmol), 4, 4'-dibromobiphenyl (1 mmol), palladium catalyst C3 (0.01 mmol), t-BuOK (3 mmol) was added to a 20 mL reaction tube, and 1.5 mL of toluene was added. Under nitrogen protection, the temperature was raised to 110 °C and stirred for 24 h. The mixture was cooled to room temperature to obtain a gray-black liquid. The mixture was precipitated in 50 mL of methanol to precipitate a gray solid, which was filtered and dried. The mixture was added to a 20 mL reaction tube and filtered. The filtrate was collected and precipitated in 50 mL of methanol for washing. The filtrate was filtered and washed twice. The washing was repeated, filtered, and dried to obtain a light yellow solid with a yield of 57.4%. After testing, the weight-average molecular weight Mw was 135241 g / mol, the molecular weight distribution index PDI was 1.69, and the structure of the long-chain alkyl polyarylamine is shown below:

[0082] .

[0083] Example 8

[0084] This embodiment provides a long-chain alkyl polyarylamine, the preparation method of which comprises the following steps:

[0085] 4-Dodecylaniline (1 mmol), 4, 4'-dibromobiphenyl (1 mmol), palladium catalyst C2 (0.02 mmol), t -BuOK (2 mmol) was added to a 20 mL reaction tube, and 1.5 mL of toluene was added. Under nitrogen protection, the temperature was raised to 100 °C and stirred for 36 h. The mixture was cooled to room temperature to obtain a gray-black liquid. The mixture was precipitated in 50 mL of methanol to precipitate a gray solid, which was filtered and dried. The mixture was added to a 20 mL reaction tube and filtered. The filtrate was collected and precipitated in 50 mL of methanol for washing. The filtrate was filtered and washed twice. The washing was repeated, filtered, and dried to obtain a light yellow solid with a yield of 62.3%. After testing, the weight-average molecular weight Mw was 33524 g / mol, the molecular weight distribution index PDI was 2.02, and the structure of the long-chain alkyl polyarylamine is shown below:

[0086] .

[0087] Example 9

[0088] This embodiment provides a long-chain alkyl polyarylamine, the preparation method of which comprises the following steps:

[0089] 4-Dodecylaniline (1 mmol), 4, 4'-dibromobiphenyl (1 mmol), palladium catalyst C1 (0.005 mmol), t-BuOK (4 mmol) was added to a 20 mL reaction tube, and 1.5 mL of toluene was added. Under nitrogen protection, the temperature was raised to 120 °C and stirred for 36 h. The mixture was cooled to room temperature to obtain a gray-black liquid. The mixture was precipitated in 50 mL of methanol to precipitate a gray solid, which was filtered and dried. The mixture was added to a 20 mL reaction tube and filtered. The filtrate was collected and precipitated in 50 mL of methanol for washing. The filtrate was filtered and washed twice. The washing was repeated, filtered, and dried to obtain a light yellow solid with a yield of 71.8%. The weight average molecular weight Mw was 25697 g / mol, the molecular weight distribution index PDI was 1.91, and the structure of the long-chain alkyl polyarylamine is shown below:

[0090] .

[0091] Example 10

[0092] This embodiment provides a long-chain alkyl polyarylamine, the preparation method of which comprises the following steps:

[0093] 4-Dodecylaniline (0.05 mmol), 4, 4'-dibromobiphenyl (0.05 mmol), palladium catalyst C3 (0.015 mmol), t -BuOK (2.5 mmol) was added to a 20 mL reaction tube, and 1.5 mL of toluene was added. Under nitrogen protection, the temperature was raised to 115 °C and stirred for 30 h. The mixture was cooled to room temperature to obtain a gray-black liquid. The mixture was precipitated in 50 mL of methanol to precipitate a gray solid, which was filtered and dried. The mixture was added to a 20 mL reaction tube and filtered. The filtrate was collected and precipitated in 50 mL of methanol for washing. The filtrate was filtered and washed twice. The washing was repeated, filtered, and dried to obtain a light yellow solid with a yield of 59.6%. After testing, the weight-average molecular weight Mw was 11531 g / mol, the molecular weight distribution index PDI was 1.41, and the structure of the long-chain alkyl polyarylamine is shown below:

[0094] .

[0095] Example 11

[0096] This embodiment provides a long-chain alkyl polyarylamine, the preparation method of which comprises the following steps:

[0097] 4-Dodecylaniline (0.5 mmol), 4, 4'-dibromobiphenyl (0.5 mmol), palladium catalyst C1 (0.008 mmol), t-BuOK (3.5 mmol) was added to a 20 mL reaction tube, and 1.5 mL of toluene was added. Under nitrogen protection, the temperature was raised to 105 °C and stirred for 18 h. The mixture was cooled to room temperature to obtain a gray-black liquid. The mixture was precipitated in 50 mL of methanol to precipitate a gray solid, which was filtered and dried. The mixture was added to a 20 mL reaction tube and filtered. The filtrate was collected and precipitated in 50 mL of methanol for washing. The filtrate was filtered and washed twice. The washing was repeated, filtered, and dried to obtain a light yellow solid with a yield of 53.8%. After testing, the weight-average molecular weight Mw was 5067 g / mol, the molecular weight distribution index PDI was 1.86, and the structure of the long-chain alkyl polyarylamine is shown below:

[0098] .

[0099] Example 12

[0100] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0101] The long-chain alkyl polyarylamine prepared in Example 4 (5 parts by mass) was mixed with polypropylene (995 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0102] Example 13

[0103] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0104] The long-chain alkyl polyarylamine prepared in Example 5 (5 parts by mass) was mixed with a polyolefin elastomer (995 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0105] Example 14

[0106] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0107] The long-chain alkyl polyarylamine prepared in Example 6 (5 parts by mass) was mixed with polyethylene (995 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0108] Example 15

[0109] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0110] The long-chain alkyl polyarylamine prepared in Example 7 (1 part by mass) was mixed with polyethylene (999 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0111] Example 16

[0112] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0113] The long-chain alkyl polyarylamine prepared in Example 7 (3 parts by mass) was mixed with polyethylene (997 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0114] Example 17

[0115] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0116] The long-chain alkyl polyarylamine prepared in Example 7 (5 parts by mass) was mixed with polyethylene (995 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0117] Example 18

[0118] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0119] The long-chain alkyl polyarylamine prepared in Example 7 (1 part by mass) was mixed with polyethylene (99 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0120] Example 19

[0121] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0122] The long-chain alkyl polyarylamine prepared in Example 7 (2 parts by mass) was mixed with polyethylene (98 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0123] Example 20

[0124] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0125] The long-chain alkyl polyarylamine prepared in Example 7 (5 parts by mass) was mixed with polyethylene (95 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0126] Example 21

[0127] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0128] The long-chain alkyl polyarylamine prepared in Example 8 (5 parts by mass) was mixed with polyethylene (995 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0129] Example 22

[0130] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0131] The long-chain alkyl polyarylamine prepared in Example 9 (5 parts by mass) was mixed with polyethylene (995 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0132] Example 23

[0133] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0134] The long-chain alkyl polyarylamine prepared in Example 10 (5 parts by mass) was mixed with polyethylene (995 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0135] Example 24

[0136] This embodiment provides a long-chain alkyl polyarylamine composite material, the preparation method of which includes the following steps:

[0137] The long-chain alkyl polyarylamine prepared in Example 11 (5 parts by mass) was mixed with polyethylene (995 parts by mass), and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a long-chain alkyl polyarylamine composite material.

[0138] Comparative Example 1

[0139] This comparative example provides a triphenylamine composite material, and its preparation method comprises the following steps:

[0140] Triphenylamine (5 parts by mass) and polyethylene (995 parts by mass) were mixed and melt-extruded at 150-220° C. to obtain a masterbatch, i.e., a triphenylamine composite material.

[0141] Comparative Example 2

[0142] This comparative example provides a MEH-PPV composite material, the preparation method of which comprises the following steps:

[0143] MEH-PPV (5 parts by mass) and polyethylene (995 parts by mass) were mixed and melt-extruded at 150-220°C to obtain a masterbatch, i.e., a MEH-PPV composite material;

[0144] The structural formula of the MEH-PPV is shown below:

[0145] ;

[0146] Among them, the number average molecular weight is 10,000~50,000.

[0147] Fluorescence testing and dispersibility testing were performed on the composite materials of Examples 12 to 14, Example 17, Examples 21 to 24, and Comparative Examples 1 to 2. The dispersibility test conditions were as follows: using dichloromethane as the dispersing solvent, with a mass ratio of dichloromethane to the composite material of 1:1, stirring at room temperature at a speed of 1000 rpm, and stirring and dispersing until the solution was clear and transparent without white spots, and the solution viscosity was stable and unchanged, indicating uniform dispersion. The shortest time required for each uniform dispersion was recorded. The results are shown in Table 1.

[0148] Table 1. Fluorescence properties of the composite materials.

[0149]

[0150] As shown in Table 1, the composite materials of long-chain alkyl polyarylamine and polyethylene in Examples 12 to 14, Example 17, and Examples 21 to 24 of the present invention have strong fluorescence intensity and good dispersion properties, and can be potentially used in fields such as display, light transfer film, and fluorescence positioning. However, the triphenylamine and MEH-PPV in Comparative Example 1 can fluoresce by themselves, but no longer fluoresce after being mixed with polyolefin.

[0151] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that after reading the specification of this application, technicians can still modify or replace the specific implementation methods of the present invention with equivalents, but these modifications or changes do not depart from the scope of protection of the pending claims of the present application.

Claims

1. A long-chain alkyl polyarylamine composite material with fluorescent properties, characterized in that: The invention comprises a long-chain alkyl polyarylamine and a polyolefin in a mass ratio of 1:19-1000, wherein the structural formula of the long-chain alkyl polyarylamine is shown in formula (I): Formula (I); Wherein, R is an alkyl group with 5 to 12 carbon atoms, the weight average molecular weight is 5000 to 136000 g / mol, and the PDI is 1.41 to 2.

24.

2. The long-chain alkyl polyarylamine composite material according to claim 1, characterized in that: The polyolefin is selected from at least one of polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyoctene, poly(4-methyl-1-pentene), and polyolefin elastomer.

3. The long-chain alkyl polyarylamine composite material according to claim 1, characterized in that: The R is pentyl, hexyl, octyl or dodecyl.

4. The long-chain alkyl polyarylamine composite material according to claim 1, characterized in that: The mass ratio of the long-chain alkyl polyarylamine to the polyolefin is 1:49-199.

5. The long-chain alkyl polyarylamine composite material according to claim 1, characterized in that: The structural formula of the long-chain alkyl polyarylamine is shown in formula (II): Formula (II); Among them, the weight average molecular weight is 5000~135241g / mol, and the PDI is 1.41~2.

02.

6. The method for preparing the long-chain alkyl polyarylamine composite material according to any one of claims 1 to 5, characterized in that: The steps include: The long-chain alkyl polyarylamine is mixed with polyolefin, and the mixture is melt-extruded to obtain the long-chain alkyl polyarylamine composite material.

7. The method for preparing the long-chain alkyl polyarylamine composite material according to claim 6, characterized in that: The temperature of the melt extrusion is 150-220°C.

8. The long-chain alkyl polyarylamine composite material according to any one of claims 1 to 5, characterized in that: The preparation method of the long-chain alkyl polyarylamine comprises the following steps: Under the action of palladium catalyst and auxiliary agent, alkyl substituted aniline and reacting with 4, 4'-dibromobiphenyl to obtain the long-chain alkyl polyarylamine.

9. The long-chain alkyl polyarylamine composite material according to claim 8, characterized in that: The structure of the palladium catalyst is shown in formula (III): Formula (III); wherein R1 and R2 are independently hydrogen, methyl, ethyl or isopropyl, and R1 and R2 are not hydrogen at the same time; And / or, the auxiliary agent includes an organic base and a solvent.

10. The long-chain alkyl polyarylamine composite material according to claim 9, characterized in that: The molar ratio of the alkyl-substituted aniline to 4, 4'-dibromobiphenyl is 1:1; and / or, the molar ratio of the palladium catalyst to 4, 4'-dibromobiphenyl is 0.005-0.02:1; And / or, the reaction temperature is 100-120° C. and the reaction time is 12-36 hours; And / or, the reaction further comprises a post-processing step after completion; and / or, the molar ratio of the 4, 4'-dibromobiphenyl to the organic base is 1:2-4; And / or, the organic base is potassium tert-butoxide; And / or, the solvent is toluene.

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