A composite material containing a dihexylfluorene-long-chain alkyl aniline polymer and a preparation method thereof

Abstract

The application discloses a kind of composite materials with fluorescent properties containing dihexylfluorene-long chain alkyl aniline polymer and preparation method thereof, belong to high polymer composite material technical field, the composite material includes the mass ratio of 1:19~1000 dihexylfluorene-long chain alkyl aniline polymer and polyolefin, the structural formula of dihexylfluorene-long chain alkyl aniline polymer in it is, the composite material solves the problem that fluorescent substance is not good in polyolefin dispersibility, and the obtained composite material has enhanced fluorescence intensity.

Description

Technical Field

[0001] This invention belongs to the field of polymer composite materials, and particularly relates to a composite material containing dihexylfluorene-long-chain alkylaniline polymer and its preparation method. Background Technology

[0002] Polyolefins are a typical general-purpose material, commonly used as matrix materials in displays, phototransfer films, and lighting. Their low cost, high chemical stability, excellent mechanical properties, and superior processability have made them widely used in daily life. However, they are inherently non-luminescent materials. Currently, methods for preparing polyolefin-based luminescent materials typically involve adding luminescent substances to the polyolefin. For example, by physically mixing fluorescent substances with polyolefins, luminescent materials with a polyolefin matrix can be prepared. However, due to the poor compatibility between fluorescent substances and polyolefins, aggregation of fluorescent substances can occur, thereby reducing the fluorescence intensity of the composite material.

[0003] Therefore, how to provide a fluorescence-enhanced polymer composite material is an urgent problem to be solved in this field. Summary of the Invention

[0004] To address the shortcomings of the prior art, a composite material containing dihexylfluorene-long-chain alkylaniline polymer and its preparation method are provided. The composite material includes dihexylfluorene-long-chain alkylaniline polymer and polyolefin, which solves the problem of poor dispersion of fluorescent substances in polyolefin. The resulting composite material has enhanced fluorescence intensity.

[0005] The purpose of this invention is to provide a composite material containing a dihexylfluorene-long-chain alkylaniline polymer, comprising a dihexylfluorene-long-chain alkylaniline polymer and a polyolefin in a mass ratio of 1:19~1000, wherein the structural formula of the dihexylfluorene-long-chain alkylaniline polymer is shown in formula (I):

[0006] Equation (Ⅰ);

[0007] Wherein, R is an alkyl group with 5 to 12 carbon atoms, a number average molecular weight of 50 kDa to 150 kDa, and a PDI of 1.5 to 3.5.

[0008] 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 elastomers.

[0009] In some embodiments of the present invention, R is pentyl, hexyl, octyl or dodecyl.

[0010] In some embodiments of the present invention, the mass ratio of the dihexylfluorene-long-chain alkylaniline polymer to the polyolefin is 1:150~300.

[0011] In some embodiments of the present invention, the dihexylfluorene-long-chain alkylaniline polymer is as shown in formula (II):

[0012] Equation (II);

[0013] Among them, the number average molecular weight is 50kDa~150kDa, and the PDI is 1.5-3.5.

[0014] In some embodiments of the present invention, the dihexylfluorene-long-chain alkylaniline polymer is as shown in formula (III):

[0015] Formula (Ⅲ);

[0016] Among them, the number average molecular weight is 80kDa~95kDa, and the PDI is 2.0~2.5.

[0017] In some embodiments of the present invention, the raw materials for preparing the dihexylfluorene-long-chain alkylaniline polymer include: long-chain alkyl-substituted aniline. and 9,9-dihexyl-2,7-dibromofluorene .

[0018] In some embodiments of the present invention, the preparation method of the dihexylfluorene-long-chain alkylaniline polymer includes the following steps:

[0019] Alkyl-substituted aniline under the action of palladium catalyst and promoter and 9,9-dihexyl-2,7-dibromofluorene The reaction occurs to obtain the dihexylfluorene-long-chain alkylaniline polymer.

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

[0021] Formula (Ⅳ);

[0022] R1 and R2 are independently hydrogen, methyl, ethyl or isopropyl, and R1 and R2 are not both hydrogen.

[0023] Another object of the present invention is to provide a method for preparing the above-mentioned composite material containing dihexylfluorene-long-chain alkylaniline polymer, comprising the following steps:

[0024] The dihexylfluorene-long-chain alkylaniline polymer is mixed with the polyolefin and melt-extruded to obtain the composite material containing the dihexylfluorene-long-chain alkylaniline polymer.

[0025] In some embodiments of the present invention, the temperature of the melt extrusion is 150~220°C.

[0026] Another object of the present invention is to provide a method for preparing the aforementioned long-chain alkyl polyarylamine composite material, comprising the following steps:

[0027] The dihexylfluorene-long-chain alkylaniline polymer and the polyolefin are dissolved in an organic solvent to obtain a mixture. The mixture is then added dropwise to an alcohol solvent to precipitate solid powder. After filtration, the composite material containing the dihexylfluorene-long-chain alkylaniline polymer is obtained.

[0028] In some embodiments of the present invention, the organic solvent includes aromatic organic solvents.

[0029] In some embodiments of the present invention, the aromatic organic solvent includes at least one of toluene, xylene, ethylbenzene, anisole, and chlorobenzene.

[0030] In some embodiments of the present invention, the alcohol solvent includes at least one of methanol and ethanol.

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

[0032] The long-chain alkyl groups in the structure of dihexylfluorene-long-chain alkylaniline polymers can improve their compatibility with polyolefins, which in turn helps composite materials containing dihexylfluorene-long-chain alkylaniline polymers to obtain good fluorescence intensity. Furthermore, polyolefins have a "molecular dispersion" effect on dihexylfluorene-long-chain alkylaniline polymers, which can reduce the intermolecular aggregation of dihexylfluorene-long-chain alkylaniline polymers and the resulting fluorescence quenching effect, thereby improving the fluorescence intensity of composite materials containing dihexylfluorene-long-chain alkylaniline polymers. Attached Figure Description

[0033] Figure 1 Solid-state fluorescence spectra of the composite material containing dihexylfluorene-long-chain alkylaniline polymer obtained in Example 1 of the present invention and the dihexylfluorene-long-chain alkylaniline polymer obtained in Preparation Example 4;

[0034] Figure 2 The DSC secondary heating curves are for the composite materials obtained in Examples 1-2 of this invention, the dihexylfluorene-long-chain alkylaniline polymer obtained in Preparation Example 4, and polypropylene.

[0035] Figure 3 The DSC cooling curves are for the composite materials obtained in Examples 1-2 of this invention and for polypropylene. Detailed Implementation

[0036] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0037] Unless otherwise specified, all raw materials used in this invention are commercially available.

[0038] Example 1

[0039] All raw materials used in this invention are commercially available.

[0040] The structure of imidazole salt ligand L1 is shown below:

[0041] ;

[0042] The structure of imidazole salt ligand L2 is shown below:

[0043] ;

[0044] The structure of imidazole salt ligand L3 is shown below:

[0045] .

[0046] Preparation Example 1

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

[0048] Imidazole salt 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 was completed, the liquid was removed under reduced pressure, and the crude product was dissolved in 5 mL of dichloromethane. Subsequently, 20 mL of n-hexane was added, and the resulting palladium complex precipitate was collected by filtration, washed with n-hexane (2 × 20 mL), and dried to obtain a grayish-white palladium catalyst powder C1 with a yield of 81%. The NMR C-H spectrum of palladium catalyst C1 is as follows:

[0049] 1H 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] Preparation Example 2

[0054] This preparation example provides a palladium catalyst C2, the preparation method of which includes 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 was completed, the liquid was removed under reduced pressure, and the crude product was dissolved in 5 mL of dichloromethane. Subsequently, 20 mL of n-hexane was added, and the resulting palladium complex precipitate was collected by filtration, washed with n-hexane (2 × 20 mL), and dried to obtain a grayish-white palladium catalyst powder C2 with a yield of 76%. The NMR C-H spectrum of palladium catalyst C2 is as follows:

[0056] 1H 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] 13 C 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] Preparation Example 3

[0061] This preparation example provides a palladium catalyst C3, the preparation method of which includes 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 was completed, the liquid was removed under reduced pressure, and the crude product was dissolved in 5 mL of dichloromethane. Subsequently, 20 mL of n-hexane was added, and the resulting palladium complex precipitate was collected by filtration, washed with n-hexane (2 × 20 mL), and dried to obtain a grayish-white palladium catalyst powder C3 with a yield of 74%. The NMR C-H spectrum of palladium catalyst C3 is as follows:

[0063] 1H 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] 13 C 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] Preparation Example 4

[0068] This preparation example provides a dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0069] 1 mmol of 4-dodecylaniline, 1 mmol of 9,9-dihexyl-2,7-dibromofluorene, and 3 mmol of KO were added to the reactor. t Bu, 0.01 mmol palladium catalyst C1, 3 mL toluene, nitrogen atmosphere, and reaction at 110 °C for 24 h. After the reaction, cool to room temperature, add dropwise to methanol solution to precipitate, wash 2-3 times with methanol solution, filter and air dry to obtain crude polymer; dissolve crude polymer in THF, stir at room temperature for 24 h, filter, add dropwise to methanol solution to precipitate, wash 2-3 times with methanol solution, filter and air dry to obtain yellow polymer, namely dihexylfluorene-long-chain alkylaniline polymer, yield 80%.

[0070] GPC analysis showed that the number-average molecular weight (Mn) was 95.60 kDa and the molecular weight distribution index (PDI) was 2.06. The structure of the long-chain alkyl polyarylamine is shown below:

[0071] .

[0072] Preparation Example 5

[0073] This preparation example provides a dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0074] 1 mmol of 4-dodecylaniline, 1.05 mmol of 9,9-dihexyl-2,7-dibromofluorene, and 3 mmol of KO were added to the reactor. t Bu, 0.01 mmol palladium catalyst C2, 3 mL toluene, nitrogen gas was introduced, and the reaction was carried out at 105 °C for 12 h. After the reaction was completed, the mixture was cooled to room temperature, added dropwise to a methanol solution to precipitate, washed 2-3 times with methanol solution, filtered, and air-dried to obtain crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the filtrate was added dropwise to a methanol solution to precipitate, washed 2-3 times with methanol solution, filtered, and air-dried to obtain a yellow polymer, namely dihexylfluorene-long-chain alkylaniline polymer, with a yield of 76%.

[0075] GPC analysis showed that the number-average molecular weight (Mn) was 56.12 kDa and the molecular weight distribution index (PDI) was 1.89. The structure of the long-chain alkyl polyarylamine is shown below:

[0076] .

[0077] Preparation Example 6

[0078] This preparation example provides a dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0079] 1 mmol of 4-dodecylaniline, 1 mmol of 9,9-dihexyl-2,7-dibromofluorene, and 3 mmol of KO were added to the reactor. t Bu, 0.02 mmol palladium catalyst C1, 3 mL toluene, nitrogen atmosphere, and reaction at 115 °C for 30 h. After the reaction, cool to room temperature, add dropwise to methanol solution to precipitate, wash 2-3 times with methanol solution, filter and air dry to obtain crude polymer; dissolve crude polymer in THF, stir at room temperature for 24 h, filter, add dropwise to methanol solution to precipitate, wash 2-3 times with methanol solution, filter and air dry to obtain yellow polymer, namely dihexylfluorene-long-chain alkylaniline polymer, yield 74%.

[0080] GPC analysis showed that the number-average molecular weight (Mn) was 136.01 kDa and the molecular weight distribution index (PDI) was 3.12. The structure of the long-chain alkyl polyarylamine is shown below:

[0081] .

[0082] Preparation Example 7

[0083] This preparation example provides a dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0084] 1 mmol of 4-octylaniline, 1 mmol of 9,9-dihexyl-2,7-dibromofluorene, and 3 mmol of KO were added to the reactor. t Bu, 0.02 mmol palladium catalyst C3, 3 mL toluene, and nitrogen atmosphere were introduced, and the reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature, added dropwise to a methanol solution to precipitate, washed 2-3 times with methanol solution, filtered, and air-dried to obtain a crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the filtrate was added dropwise to a methanol solution to precipitate, washed 2-3 times with methanol solution, filtered, and air-dried to obtain a yellow polymer, namely dihexylfluorene-long-chain alkylaniline polymer, with a yield of 78%.

[0085] GPC analysis showed that the number-average molecular weight (Mn) was 87.25 kDa and the molecular weight distribution index (PDI) was 2.25. The structure of the long-chain alkyl polyarylamine is shown below:

[0086] .

[0087] Preparation Example 8

[0088] This preparation example provides a dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0089] 1 mmol of 4-hexylaniline, 1 mmol of 9,9-dihexyl-2,7-dibromofluorene, and 3 mmol of KO were added to the reactor. t Bu, 0.02 mmol palladium catalyst Cl, 3 mL toluene, nitrogen atmosphere, and reaction at 110 °C for 24 h. After the reaction, cool to room temperature, add dropwise to methanol solution to precipitate, wash 2-3 times with methanol solution, filter and air dry to obtain crude polymer; dissolve crude polymer in THF, stir at room temperature for 24 h, filter, add dropwise to methanol solution to precipitate, wash 2-3 times with methanol solution, filter and air dry to obtain yellow polymer, namely dihexylfluorene-long-chain alkylaniline polymer, yield 82%.

[0090] GPC analysis showed that the number-average molecular weight (Mn) was 78.54 kDa and the molecular weight distribution index (PDI) was 2.83. The structure of the long-chain alkyl polyarylamine is shown below:

[0091] .

[0092] Preparation Example 9

[0093] This preparation example provides a dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0094] 1 mmol of 4-pentylaniline, 1 mmol of 9,9-dihexyl-2,7-dibromofluorene, and 3 mmol of KO were added to the reactor. t Bu, 0.02 mmol palladium catalyst C2, 3 mL toluene, and nitrogen atmosphere were introduced, and the reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature, added dropwise to a methanol solution to precipitate, washed 2-3 times with methanol solution, filtered, and air-dried to obtain a crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the filtrate was added dropwise to a methanol solution to precipitate, washed 2-3 times with methanol solution, filtered, and air-dried to obtain a yellow polymer, namely dihexylfluorene-long-chain alkylaniline polymer, with a yield of 82%.

[0095] GPC analysis showed that the number-average molecular weight (Mn) was 71.89 kDa and the molecular weight distribution index (PDI) was 2.65. The structure of the long-chain alkyl polyarylamine is shown below:

[0096] .

[0097] Comparative Preparation Example 1

[0098] This comparative preparation example provides a dihexylfluorene polymer, the preparation method of which includes the following steps:

[0099] 2 mL of distilled water, 1 mL of saturated Na₂CO₃ solution, 0.05 g of tetrabutylammonium bromide, 5 mL of toluene, 0.01 g of Pd(PPh₃)₄, and 0.25 g of 2-bromo-9,9-dihexylfluorene-7-boric acid were added to a reactor. Nitrogen gas was introduced, and the reaction was carried out at 80 °C for 72 h. After the reaction was completed, the mixture was cooled to room temperature and added dropwise to a methanol solution to precipitate. The precipitate was washed 2-3 times with methanol solution, filtered, and air-dried to obtain a crude polymer. The crude polymer was dissolved in THF, added dropwise to a methanol solution to precipitate, washed 2-3 times with methanol solution, filtered, and air-dried to obtain a yellow polymer, i.e., dihexylfluorene polymer, with a yield of 77%.

[0100] GPC analysis showed that the number-average molecular weight (Mn) was 73.58 kDa and the molecular weight distribution index (PDI) was 2.42. The structure of the dihexylfluorene polymer is shown below:

[0101] .

[0102] Example 1

[0103] This embodiment provides a composite material containing dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0104] By weight, 5 parts of the dihexylfluorene-long-chain alkylaniline polymer prepared in Preparation Example 4 were mixed with 995 parts of polypropylene and melt-extruded at 150~220°C to obtain masterbatch, which is a composite material containing dihexylfluorene-long-chain alkylaniline polymer.

[0105] Example 2

[0106] This embodiment provides a composite material containing dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0107] By weight, 5 parts of the dihexylfluorene-long-chain alkylaniline polymer prepared in Preparation Example 4 and 995 parts of polypropylene were added to 10,000 parts of xylene. The mixture was heated to about 125°C while stirring until it was completely dissolved to obtain a mixture. While hot, the mixture was slowly added to methanol, and a solid precipitated out. The solid was filtered and washed twice with methanol to obtain a wet powder. The wet powder was dried to obtain a composite material containing the dihexylfluorene-long-chain alkylaniline polymer.

[0108] Example 3

[0109] This embodiment provides a composite material containing dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0110] By weight, 1 part of the dihexylfluorene-long-chain alkylaniline polymer prepared in Preparation Example 4 was mixed with 999 parts of polyethylene and melt-extruded at 150~220°C to obtain masterbatch, which is a composite material containing dihexylfluorene-long-chain alkylaniline polymer.

[0111] Example 4

[0112] This embodiment provides a composite material containing dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0113] By weight, 10 parts of the dihexylfluorene-long-chain alkylaniline polymer prepared in Preparation Example 4 were mixed with 800 parts of polyolefin elastomer and melt-extruded at 150~220°C to obtain masterbatch, which is a composite material containing dihexylfluorene-long-chain alkylaniline polymer.

[0114] Example 5

[0115] This embodiment provides a composite material containing dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0116] By weight, 15 parts of the dihexylfluorene-long-chain alkylaniline polymer prepared in Preparation Example 5 were mixed with 600 parts of polypropylene and melt-extruded at 150~220°C to obtain masterbatch, which is a composite material containing dihexylfluorene-long-chain alkylaniline polymer.

[0117] Example 6

[0118] This embodiment provides a composite material containing dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0119] By weight, 20 parts of the dihexylfluorene-long-chain alkylaniline polymer prepared in Preparation Example 6 were mixed with 500 parts of polypropylene and melt-extruded at 150~220°C to obtain masterbatch, which is a composite material containing dihexylfluorene-long-chain alkylaniline polymer.

[0120] Example 7

[0121] This embodiment provides a composite material containing dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0122] By weight, 5 parts of the dihexylfluorene-long-chain alkylaniline polymer prepared in Preparation Example 7 were mixed with 995 parts of polypropylene and melt-extruded at 150~220°C to obtain masterbatch, which is a composite material containing dihexylfluorene-long-chain alkylaniline polymer.

[0123] Example 8

[0124] This embodiment provides a composite material containing dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0125] By weight, 5 parts of the dihexylfluorene-long-chain alkylaniline polymer prepared in Preparation Example 8 were mixed with 995 parts of polypropylene and melt-extruded at 150~220°C to obtain masterbatch, which is a composite material containing dihexylfluorene-long-chain alkylaniline polymer.

[0126] Example 9

[0127] This embodiment provides a composite material containing dihexylfluorene-long-chain alkylaniline polymer, the preparation method of which includes the following steps:

[0128] By weight, 5 parts of the dihexylfluorene-long-chain alkylaniline polymer prepared in Preparation Example 9 were mixed with 995 parts of polypropylene and melt-extruded at 150~220°C to obtain masterbatch, which is a composite material containing dihexylfluorene-long-chain alkylaniline polymer.

[0129] Comparative Example 1

[0130] This comparative example provides a fluorene composite material, the preparation method of which includes the following steps:

[0131] By weight, 5 parts of the dihexylfluorene polymer prepared in Comparative Preparation Example 1 were mixed with 995 parts of polypropylene and melt-extruded at 150~220°C to obtain masterbatch, i.e. fluorene composite material.

[0132] Comparative Example 2

[0133] This comparative example provides a long-chain alkylaniline composite material, the preparation method of which includes the following steps:

[0134] By weight, 5 parts of long-chain alkyl aniline polymer are mixed with 995 parts of polypropylene and melt-extruded at 150~220℃ to obtain masterbatch, i.e. long-chain alkyl aniline composite material.

[0135] The structural formula of the long-chain alkylaniline polymer is as follows: R is a C12 straight-chain alkyl group, and M is a weight-average molecular weight. w The concentration was 135241 g / mol, and the molecular weight distribution index (PDI) was 1.69.

[0136] Performance testing

[0137] 1. Fluorescence properties

[0138] The solid-state fluorescence properties of the composite materials obtained in Examples 1-9 and Comparative Examples 1-2, as well as the dihexylfluorene-long-chain alkylaniline polymer obtained in Preparation Example 4, the dihexylfluorene polymer obtained in Comparative Example 1, and the long-chain alkylaniline polymer used in Comparative Example 2 were tested. The excitation wavelength was 380 nm, and the results are recorded in Table 1 and... Figure 1 As shown.

[0139] Table 1: Solid-state fluorescence properties

[0140]

[0141] 2. Compatibility test

[0142] The composite materials obtained in Examples 1 and 2, as well as the dihexylfluorene-long-chain alkylaniline polymer and polypropylene (denoted as "PP") prepared in Example 4, were subjected to DSC analysis, and their secondary heating curves are shown below. Figure 2 As shown, the cooling curve is as follows Figure 3 As shown.

[0143] According to Table 1 and Figure 1It is evident that the composite materials containing dihexylfluorene-long-chain alkylaniline polymers obtained in Examples 1-9 of this invention exhibit enhanced fluorescence intensity compared to the dihexylfluorene-long-chain alkylaniline polymer itself. In particular, the composite materials containing dihexylfluorene-long-chain alkylaniline polymers in Examples 1-7, prepared using dihexylfluorene-long-chain alkylaniline polymers with C8 or C12 alkyl chains, have a fluorescence intensity approximately twice that of the dihexylfluorene-long-chain alkylaniline polymer itself. In contrast, the composite materials obtained in Comparative Examples 1-2 use dihexylfluorene polymers or long-chain alkylaniline polymers. These polymers generally have poor compatibility and dispersibility with polyolefins, and polyolefins cannot achieve a "molecular dispersion" effect. Therefore, the fluorescence intensity of the resulting composite materials is lower than that of the dihexylfluorene polymer or the long-chain alkylaniline polymer itself; that is, the enhanced fluorescence intensity of the composite material cannot be achieved.

[0144] according to Figure 2 The secondary heating curves show that under melt blending conditions, the dihexylfluorene-long-chain alkylaniline polymer causes a slight decrease in the crystallinity of polypropylene while maintaining a relatively constant crystallization temperature. Under solution blending conditions, the dihexylfluorene-long-chain alkylaniline polymer has little effect on the crystallization temperature of polypropylene, and may even slightly increase the crystallinity. This indicates that the dihexylfluorene-long-chain alkylaniline polymer and polypropylene have good interfacial compatibility and mild structural disturbance. Furthermore, according to... Figure 3 The cooling curves show that, under melt blending conditions, although the dihexylfluorene-long-chain alkylaniline polymer did not lower the crystallization peak temperature (Tc remained unchanged), the broadening of the half-peak width indicates that it made the crystallization process more dispersed and partially disrupted the uniformity of the system, but the degree of disturbance was small and the compatibility was good. Under solution blending conditions, the half-peak width became narrower and the crystallization peak temperature remained basically unchanged, indicating that the crystallization process was more concentrated and more uniform. It can be considered that the solution blending method is more favorable to the phase / dispersion state of both.

[0145] 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, those skilled in the art should understand that after reading this application specification, they can still modify or make equivalent substitutions to the specific implementation of the present invention, but these modifications or changes do not depart from the protection scope of the pending claims of the present invention.

Claims

1. A composite material containing a dihexylfluorene-long-chain alkylaniline polymer with fluorescent properties, characterized in that, The mixture comprises a dihexylfluorene-long-chain alkylaniline polymer and a polyolefin in a mass ratio of 1:19 to 1000, wherein the structural formula of the dihexylfluorene-long-chain alkylaniline polymer is shown in formula (I): Equation (Ⅰ); Wherein, R is an alkyl group with 5 to 12 carbon atoms, a number average molecular weight of 50 kDa to 150 kDa, and a PDI of 1.5 to 3.

5.

2. The 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 elastomers.

3. The composite material according to claim 1, characterized in that, R is pentyl, hexyl, octyl, or dodecyl.

4. The composite material according to claim 1, characterized in that, The mass ratio of the dihexylfluorene-long-chain alkyl aniline polymer to the polyolefin is 1:150~300.

5. The composite material according to claim 1, characterized in that, The dihexylfluorene-long-chain alkylaniline polymer is shown in formula (II): Equation (II); Among them, the number average molecular weight is 50kDa~150kDa, and the PDI is 1.5-3.

5.

6. The composite material according to claim 1, characterized in that, The dihexylfluorene-long-chain alkylaniline polymer is shown in formula (III): Formula (Ⅲ); Among them, the number average molecular weight is 80kDa~95kDa, and the PDI is 2.0~2.

5.

7. The composite material according to claim 1, characterized in that, The raw materials for preparing the dihexylfluorene-long-chain alkyl aniline polymer include: long-chain alkyl-substituted aniline. and 9,9-dihexyl-2,7-dibromofluorene .

8. The composite material according to claim 1, characterized in that, The preparation method of the dihexylfluorene-long-chain alkylaniline polymer includes the following steps: Alkyl-substituted aniline under the action of palladium catalyst and promoter and 9,9-dihexyl-2,7-dibromofluorene The reaction occurs to obtain the dihexylfluorene-long-chain alkylaniline polymer.

9. A method for preparing the composite material containing dihexylfluorene-long-chain alkylaniline polymer according to any one of claims 1 to 8, characterized in that, Includes the following steps: The dihexylfluorene-long-chain alkylaniline polymer is mixed with the polyolefin and melt-extruded to obtain the composite material containing the dihexylfluorene-long-chain alkylaniline polymer.

10. A method for preparing the composite material containing dihexylfluorene-long-chain alkylaniline polymer according to any one of claims 1 to 8, characterized in that, Includes the following steps: The dihexylfluorene-long-chain alkylaniline polymer and the polyolefin are dissolved in an organic solvent to obtain a mixture. The mixture is then added dropwise to an alcohol solvent to precipitate solid powder. After filtration, the composite material containing the dihexylfluorene-long-chain alkylaniline polymer is obtained.

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